KR20190087532A - A method of dyeing keratin fibers using at least one specific triarylmethane dye and at least one fluorescent dye - Google Patents

Abstract

A process for dyeing keratin fibers using at least one specific triarylmethane dye and at least one fluorescent dye. The present invention relates to a process for dyeing keratin fibers, in particular human keratin fibers, such as hair, using one or more specific triarylmethane dyes and one or more fluorescent dyes. The present invention also relates to a cosmetic composition comprising a dye as defined above and also to a multi-compartment device containing said dye. The present invention also relates to a process for the production of bright keratin fibers, in particular human keratin fibers, such as hair, in the form of a chestnut-brown, a dark chestnut-brown, a brown, a shiny brown , Or even black. ≪ / RTI >

Description

A method of dyeing keratin fibers using at least one specific triarylmethane dye and at least one fluorescent dye

The present invention relates to a method of dyeing keratin fibers, in particular human keratin fibers, such as hair, using one or more specific triarylmethane dyes and one or more fluorescent dyes.

The present invention also relates to a cosmetic composition comprising a dye as defined above and also to a multi-compartment device containing said dye.

The present invention also relates to a method for the production of light keratin fibers, in particular human keratin fibers, for example hair, in the form of chestnut-brown, To dark chestnut-brown, brown, brown with a glint, or even black.

Many have long been trying to change people's hair color and especially hide their gray hair.

It is a particularly common practice to dye keratin fibers, in particular human keratin fibers, with dye compositions containing oxidative dye precursors, commonly known as oxidation bases. Such an oxidation base is a colorless or lightly colored compound, which, when combined with an oxidation product, can produce a colored compound through an oxidative condensation process.

The color tone obtained with this oxidation base can be changed by combining these with a coupler or color modifier. Various molecules used as oxidation bases and couplers enable a wide range of colors to be obtained.

Another well-known method consists in obtaining semi-permanent dyeing by applying direct dyes to the keratinous fibers, which are colored and coloring molecules with affinity for the fibers.

Commonly used direct dyes are selected from nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine and triarylmethane direct dyes. The species may be non-ionic, anionic (acidic dye) or cationic (basic dye). Direct dyes can also be natural dyes.

Conventional direct dyeing processes consist of applying a dye composition comprising a dye directly to keratin fibers. After application, the leave-on time is observed to allow dye molecules to penetrate by diffusion into the fibers. At the end of the process, the fibers are cleaned.

Unlike oxidation dyeing, this direct dyeing process tends to better protect the integrity of the fiber. The resulting coloration is generally chromatic, but only semi-transient. The nature of the interaction of directly binding the dyes to the keratin fibers and their desorption from the surface and / or core of the fibers causes its weak dyeing power.

Although a wide range of colors are currently available, it has generally been demonstrated that to obtain a natural hue, the combination of three complementary color dyes, the principle of three primary colors is required (see, for example, WO 95/15144 and WO 95 / 01772). However, the combination of these three colors does not exhibit good persistence for repeated shampooing. This in general, or even systematically, induces a non-aesthetic change in color that consumers are reluctant to.

Also, such staining may not be fast enough, despite external agents, for example light or perspiration.

This makes it particularly possible to achieve a natural color without the abovementioned disadvantages, in particular in particular in terms of chromaticity, staining power, strength, sheen and selectivity, It is in fact required to carry out a direct dyeing process of keratin fibers, especially human keratin fibers, for example, hair, which is continuous with the hair.

It is therefore a further object of the present invention to provide a method of making bright keratin fibers by effectively blending bright keratin fibers with chestnut-brown, dark chestnut-brown, brown or even brilliant brown or even black by mixing direct dyes and preferably only two types of direct dyes To be dyed.

The Applicant has surprisingly found that the process of dyeing keratin fibers using one or more specific triarylmethane dyes and one or more specific fluorescent dyes achieves the above-mentioned object, in particular the use of a shampoo- Natural chestnut-brown, dark chestnut-brown, brown, shiny brown or even black color.

One subject of the present invention is, in particular, a process for dyeing keratin fibers, in particular human keratin fibers, for example hair, which comprises applying the keratin fibers to the keratin fibers,

(a) a compound selected from the group consisting of compounds of the following general formula (I), optical isomers thereof, geometric isomers thereof, tautomers thereof, organic or inorganic, acid or base salts thereof, solvates thereof such as hydrates, Triarylmethane dyes; And

(b) applying as fluorescent dyes one or more of the components of a fluorescent dye that is a direct dye selected from cyanine dyes, styryl / hemicyanide dyes, naphthalimide dyes, and mixtures thereof,

Wherein the triarylmethane dye (s) (a) and the fluorescent dye (s) (b) are understood to be applied to the keratinous fibers together or sequentially:

(I)

In the above formula (I)

R ₁ , R ₂ , R ' ₁ and R ₂ may be the same or different,

Hydrogen atom,

- optionally substituted and / or

- at least one heteroatom, preferably oxygen or sulfur, and / or at least one heteroatom, preferably oxygen, sulfur, C (O), SO, SO ₂ and SO ₃ ^- Optionally substituted with one or more groups comprising at least one heteroatom selected from < RTI ID = 0.0 >

Linear or branched C ₁ to C ₂₀ alkyl radicals,

A benzyl radical optionally substituted with one or more SO ₃ ^- or SO ₃ H groups;

R ₃ and R ' ₃ may be the same or different and independently of one another:

Linear or branched C ₁ to C ₆ alkyl radicals;

○ sulfonate group SO ₃ ^- , or

A sulfone group SO ₃ H;

N and m may be the same or different and represent two integers ranging from 0 to 4;

Radicals R < ₄ > may be the same or different and independently of one another:

Linear or branched C ₁ to C ₆ alkyl radicals,

○ Hydroxyl radical,

○ SO ₃ ^- ,

○ SO ₃ H,

A halogen atom, preferably a chlorine atom,

Alternatively, two adjacent radicals R ₄ together form an unsaturated six-membered ring, preferably an aromatic ring, such as benzo, optionally substituted with one or more SO ₃ ^- or SO ₃ H groups ;

Q is an integer ranging from 0 to 4;

R ₅ is

Hydrogen atom,

A halogen atom, preferably a chlorine atom,

○ Amino radical,

○ Hydroxyl radical,

- an electron-withdrawing group, for example SO ₃ ^- or SO ₃ H, through a mesomeric effect, or

Radicals -NR ₆ R ₇ wherein R ₆ and R ₇ , which may be the same or different,

- a hydrogen atom,

- represents a linear or branched C ₁ to C ₆ alkyl radical;

this is

The radicals R ₂ are present or absent and are symbolized by a dotted bond, and when R ₂ is present, the nitrogen atom having it has a cationic ammonium form and when R ₂ is absent, the nitrogen atom with it is not charged , (+) Does not exist,

● a compound of formula (I) optionally, one or more anion An ^- and optionally comprising at least one cation M ⁺ in order to ensure the electrical neutrality of the molecule;

- An ^- is an anion, preferably, bromide, chloride, represents a negative ion selected from a mixture of methyl sulfate, toluene sulfonate ion or the ion;

- M ⁺ is understood to denote a cation selected from a cation, preferably sodium, potassium, magnesium, calcium, zinc and ammonium ions or a mixture of such ions.

Another subject of the invention is

(a) compounds of formula (I) as defined above and also optical isomers thereof, geometric isomers thereof, tautomers thereof, organic or inorganic acid or base salts thereof, solvates thereof, such as hydrates, One or more triarylmethane dyes selected from mixtures of And

(b) at least one fluorescent dye as defined above.

The combination of specific triarylmethane dye (s) and fluorescent dye (s) makes it particularly possible to obtain natural colors with good dyeing properties, in particular in terms of chromaticity, dying power, strength, gloss and selectivity.

The processes and compositions according to the present invention can also be used to produce direct dyes and, in particular, dyes (a) and dyes only as defined above, without the need to use additional (or complementary) dyes other than (a) (b), it is possible to efficiently dye bright keratin materials into chestnut-brown, dark chestnut-brown, brown, shiny brown or even black.

In addition, the hues obtained by the processes and compositions according to the invention show good resistance to a variety of attack factors, such as light, bad weather, washing and perspiration, which hair may suffer. This is especially true for tines, especially after at least three shampoo washes.

The subject of the present invention is also the compounds of formula (I) as defined above, and also their optical isomers, their geometric isomers, their tautomers, their organic or inorganic acid or base salts, their solvates, And a second compartment containing one or more fluorescent dyes (b) as defined above, and a second compartment containing one or more triarylmethane dyes (a) .

Another subject of the present invention is the use of bright keratin fibers, in particular human keratin fibers, such as, for example, chestnut-brown, dark chestnut-brown, brown, (I) as defined hereinbefore for dyeing with glittering brown or even black, and also optical isomers thereof, geometric isomers thereof, tautomers thereof, organic or inorganic acid or base salts thereof, solvates thereof (S) as defined above in combination with a triarylmethane dye (s) selected from, for example, hydrates, and mixtures thereof.

Other subjects, features, aspects and advantages of the present invention will become more apparent upon reading the following description and examples.

For purposes of the present invention and unless otherwise specified:

" Dyes " according to the invention absorb light in the visible range, i. _{E. In particular} at a wavelength? _Abs of 400 to 700 nm (inclusive).

For the purposes of the present invention, the term " direct dye " refers to natural and / or synthetic dyes, which in addition to oxidation dyes are soluble in cosmetic media, which is a dye that diffuses superficially on the keratinous fibers.

For the purposes of the present invention, the term " fluorescent dye " is a colored molecule (which absorbs visible light), which itself gives a color and which absorbs the energy absorbed in the visible portion of the spectrum, as opposed to a universal dye. ≪ / RTI > to a longer wavelength of light; In particular, the " fluorescent " dyes of the present invention absorb light in the visible range at wavelengths λ _abs of 350 to 800 nm and re-emit at 400 to 800 nm in the visible range at wavelength λ _em longer than that absorbed Can be; Also known as Stoke's shift, the difference between the absorption and emission wavelengths is from 1 nm to 100 nm. More preferably, the fluorescent dye of the present invention is a dye capable of absorbing at a wavelength? _Abs of 420 to 550 nm and releasing it again in a visible range at a wavelength? _Em of 470 to 600 nm.

" Fluorescent dyes " according to the present invention should be distinguished from optical brighteners. "Brighteners" or "fluorescent whitening agent (fluorescent brightening agent)" or "fluorescent whitening screen agents (fluorescent whitening agent) or FWA" or also known as "whitening agent (whitener)" or "fluorescent whitening agent", optical brighteners are generally , As a colorless compound, which does not impart color, and consequently, absorbs and absorbs the energy only in the ultraviolet range (wavelength in the range of 200 to 400 nm) without absorbing it in the visible range, It is not a dye because it converts it into fluorescent light of longer wavelength emitted from. The color impression is subsequently generated only by fluorescent light, which is mainly blue (wavelength in the range of 400 to 500 nm).

■ in accordance with the present invention, "Blue-violet (blue-violet)" The dye absorbs light in the visible spectrum, and visually representing a blue color, i.e., 550 nm greater than and 700 absorption wavelength in nm below λ _max, in particular 560 nm as to 700 nm, preferably, in the blue range λ _max that is, dyes that absorb light in the 580 to 650 nm for λ _max.

" (Hetero) aryl " means aryl and heteroaryl groups;

The " aryl " or " heteroaryl " radical or the aryl or heteroaryl portion of the radical may be substituted with at least one substituent having a carbon atom selected from:

- a hydroxyl, C ₁ -C ₂ alkoxy, C ₂ -C ₄ (poly) hydroxy alkoxy, acylamino, and optionally having the same or different and may be a group as at least one hydroxyl group, the two C ₁ -C ₄ alkyl A C ₁ -C ₆ and preferably a C ₁ -C ₄ alkyl radical optionally substituted with one or more radicals selected from amino substituted by a radical selected from the group consisting of hydrogen, Two radicals which may form a saturated or unsaturated, optionally substituted 5- to 7-membered and preferably 5-or 6-membered heterocycle,

A halogen atom, for example, chlorine;

- a hydroxyl or thiol group;

- C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkylthio radical;

- (poly) hydroxy (C ₂ -C ₆ ) alkoxy radical;

- amino radical;

- (C ₁ -C ₄ ) alkyl radical, a 5-or 6-membered heterocycloalkyl radical, preferentially substituted by methyl, preferentially morpholino, piperazino, piperidino or pyrrolidino;

- a (C ₁ -C ₄ ) alkyl radical, preferably a 5-or 6-membered heteroaryl radical optionally substituted by methyl, preferentially imidazolyl;

An amino radical substituted with one or two identical or different C ₁ -C ₆ alkyl radicals, optionally at least:

  i) a hydroxyl group,

ii) an amino group optionally substituted by one or two optionally substituted C ₁ -C ₃ alkyl radicals, wherein said alkyl radical, together with the nitrogen atom to which it is attached, contains at least one other nitrogen or non-nitrogen heteroatom Optionally, a saturated or unsaturated, optionally substituted 5 to 7 membered heterocycle,

iii) 4 quaternary ammonium group ^{-N + R'R "R"',} M - ( wherein, R', R "and R"'may be the same or different, represent a C ₁ -C ₄ alkyl, M ^- Represents an anionic counterion), or

iv) a (C ₁ -C ₄ ) alkyl radical, preferentially a cationic 5-membered or 6-membered heteroaryl radical optionally substituted by methyl, preferentially imidazolium;

- acylamino radical (-N (R) -C (O ) -R ') ( wherein, R radical is a hydrogen atom or at least one hydroxyl group with C ₁ -C ₄ alkyl radical, R' radicals are C ₁ C ₂ alkyl radical);

-Carbamoyl radical ((R) ₂ NC (O) -), where the radicals R can be the same or different and are hydrogen atoms or C ₁ -C ₄ alkyl radicals optionally having at least one hydroxyl group );

-Alkylsulfonylamino radical (R'-S (O) ₂ -N (R) -), wherein the radical R represents a hydrogen atom or a C ₁ -C ₄ alkyl radical optionally having at least one hydroxyl group, R 'radical represents a C ₁ -C ₄ alkyl radical, or a phenyl radical;

-Aminosulfonyl radical ((R) ₂ NS (O) _2- ), wherein the radicals R can be the same or different and are hydrogen atoms or C ₁ -C ₄ alkyl radicals optionally having at least one hydroxyl group Lt; / RTI >

- carboxyl radicals in acid or chloride form (preferably alkali metal or substituted or unsubstituted ammonium);

- cyano group;

A nitro or nitroso group;

A polyhaloalkyl group, preferably trifluoromethyl;

The cyclic or heterocyclic of the non-aromatic radical may be substituted with at least one substituent selected from the following groups:

- hydroxyl;

- C ₁ -C ₄ alkoxy, C ₂ -C ₄ (poly) hydroxyalkoxy;

- C ₁ -C ₄ alkyl;

Wherein the radical R 'is a C ₁ -C ₄ alkyl radical optionally having a hydrogen atom or at least one hydroxyl group, and the radical R is C (O) -N (R') - _A C ₁ -C ₂ alkyl radical or an amino radical optionally substituted with one or two C ₁ -C ₄ alkyl groups which may be the same or different and themselves optionally carry at least one hydroxyl group, Together with the nitrogen atom to which they are attached may form a saturated or unsaturated, optionally substituted 5 to 7 membered heterocycle optionally comprising at least one other nitrogen or non-nitrogen heteroatom);

Wherein the radical R is a C ₁ -C ₄ alkyl radical or one or two identical or different C (O) -O- groups optionally having at least one hydroxyl group, An amino group optionally substituted with _{1 to 4} alkyl groups, said alkyl radical optionally substituted with saturated or unsaturated, optionally substituted, optionally containing at least one other nitrogen or non-nitrogen heteroatom in combination with the nitrogen atom to which it is attached Lt; RTI ID = 0.0 > 5-7 < / RTI > membered heterocycle);

Wherein R is a C ₁ -C ₄ alkoxy radical and X is an oxygen atom or a C ₁ -C ₄ alkyl optionally having at least one hydroxyl group, An optionally substituted amino group optionally substituted with at least one other nitrogen or non-nitrogen heteroatom in addition to the nitrogen atom to which the alkyl radical is attached, Lt; / RTI > may form a heterocycle;

A cyclic or heterocyclic radical, or a non-aromatic portion of an aryl or heteroaryl radical, which may also be substituted with one or more oxo groups;

An " aryl " radical represents a monocyclic or fused or non-fused polycyclic carbon-based group containing from 6 to 22 carbon atoms, at least one of which is aromatic; Preferentially, the aryl radical is phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl;

" Cationic heteroaryl radical " is a heteroaryl group as defined above, including an inward ring or an outward ring cationic group,

- when the charge is an inward loop, it is included in the electron fractionation through the mesomer effect; For example, it is a pyridinium, imidazolium or indolinium group:

Wherein R and R 'are heteroaryl substituents as defined above and especially (hydroxy) (C ₁ -C ₈ ) alkyl groups such as methyl;

When the charge is an outward loop, it is not included in the electron fractionation through the mesomer effect; For example, it is trimethylammonium outside the ammonium or phosphonium substituent R ^& lt ^{; +} & gt ^; , for example heteroaryl, for example pyridyl, indolyl, imidazolyl or naphthalimidyl,

Wherein R is a heteroaryl substituent as defined below and R ⁺ is an ammonium R _a R _b R _c N ⁺ -, a phosphonium R _a R _b R _c P ⁺ - or an ammonium R _a R _b R _{c ^{N + - (C 1 -C 6}} ) _{alkylamino, R a R b R c N} + - (C 1 -C 6) alkyl or ^{_{R a R b R c N +}} - (C 1 -C 6) alkoxy group , Wherein R _a , R _b and R _c , which may be the same or different, represent a (C ₁ -C ₈ ) alkyl group, for example methyl;

" Heteroaryl radical " refers to a 5- to 22-membered monocyclic or fused or non-fused polycyclic group containing one to six heteroatoms selected from nitrogen, oxygen and sulfur, of which at least one The ring is aromatic; Preferentially, the heteroaryl radical is selected from the group consisting of acridinyl, benzimidazolyl, benzo bistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetra Wherein the heteroaryl group is selected from the group consisting of pyridyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, Pyridyl, pyridino, imidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazolylpiperidinyl, Thiazolyl, imidazolyl, thiazolyl, imidazolyl, thiopyryl, triazolyl, zantilyl, and ammonium salts thereof;

" Heterocyclic radical " refers to a monocyclic or fused or non-fused, polycyclic, monocyclic, or bicyclic, monocyclic or bicyclic monocyclic, bicyclic or tricyclic ring containing one or two heteroatoms selected from nitrogen, A radical which is a 5- to 22-membered non-aromatic radical;

" Heterocycloalkyl radical " is a heterocyclic radical comprising at least one saturated ring;

" Alkyl radical " is generally a linear or branched C ₁ to C ₂₀ , preferably C ₁ to C ₁₀ , more preferably C ₁ to C ₈ , more preferably C ₁ to C ₆ and better , A C ₁ to C ₄ hydrocarbon-based radical;

The expression " optionally substituted " applied to an alkyl radical means that said alkyl radical can be substituted with one or more radicals selected from the following radicals: i) hydroxyl, ii) C ₁ -C ₄ alkoxy, iii) RZC (X) -Y- wherein X, Y and Z represent an oxygen or sulfur atom or N (R ') or, alternatively, X and / or Z represents a bond, R and R' Optionally substituted with one or two identical or different C ₁ -C ₄ alkyl radicals, optionally substituted with one or two identical or different C ₁ -C ₄ alkyl radicals, which may be different or different and represent hydrogen atoms or (C ₁ -C ₆ ) alkyl groups, preferably X represents an oxygen atom; Wherein the alkyl radical, together with the nitrogen atom having it, may form a 5- to 7-membered heterocycle optionally containing another nitrogen or non-nitrogen heteroatom; Or v) a quaternary ammonium group N ⁺ R'R "R"', M ^- , wherein R', R "and R '' may be the same or different and represent a C ₁ -C ₄ alkyl group, , -N ⁺ R'R "R "'forms a heteroaryl, for example, an imidazolium optionally substituted with a C ₁ -C ₄ alkyl group, and M ^- represents an anionic counterion) vi) carboxylic C (O) OH, vii) carboxylate, ^{C (O) O -, M} + ( wherein, M ⁺ represents a cationic counter ion, for example, alkali metal or alkaline earth metal), viii) Sulfone-SO ₃ H, ix) sulfonate -SO ₃ ^- , M ⁺ , wherein M ⁺ is as defined above, and x) cyano;

■ "alkoxy radical" is an alkyl radical is a linear or branched C ₁ -C _8, and preferentially, C ₁ -C ₆ hydrocarbon-based radical of an alkyl-oxy radical;

When the alkoxy group is optionally substituted, it means that the alkyl group is optionally substituted as defined above;

■ The term "organic or inorganic acid salts" More specifically, i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H ₂ SO _4, iv) an alkyl sulfonic acid: for _{Alk-S (O) 2 OH} , for example , Methanesulfonic acid and ethanesulfonic acid; v) Arylsulfonic acids: Ar-S (O) ₂ OH, for example benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) alkoxysulfinic acid: Alk-OS (O) -OH, for example, methoxy fins acid and ethoxy fins acid; xi) aryloxy fins acids such as, for example, toluenoxymethyl finsic acid and phenoxy fins acid; xii) phosphoric acid H ₃ PO _4; xiii) acetic acid CH ₃ C (O) -OH; xiv) triflic acid CF ₃ SO ₃ H; And xv) a salt selected from salts derived from tetrafluoroboric acid HBF ₄ ;

The term " anionic counterion " means an anionic or anionic group derived from an organic or inorganic acid that counteracts the cationic charge of the dye; More specifically, the anionic counterion is i) a halide, such as chloride or bromide; ii) nitrate; iii) C ₁ -C ₆ alkyl _{sulfonate: Alk-S (O) 2} O -, for example, a sulfonyl containing methyl sulphonate or mesylate, ethyl sulfonate and sulfonate; iv) aryl _{sulfonates: Ar-S (O) 2} O -, e.g., benzenesulfonate and toluenesulfonate or tosylate; v) carboxylate Alk-C (O) -OH wherein Alk represents one or more hydroxyl or carboxylate groups, for example a (C ₁ -C ₆ ) alkyl group optionally substituted by citrate, ; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: Alk-OS (O) O -, for example, methyl sulfate and ethyl sulfate; x) aryl sulfates: Ar-OS (O) O -, for example, benzene sulfate and toluene sulfate; xi) alkoxy _{sulfates: Alk-OS (O) 2} O -, for example, methoxy sulfate and ethoxy sulfate; xii) aryloxy _{sulfates: Ar-OS (O) 2} O -, xiii) phosphate, _{O = P (OH) 2 -O} -, O = P (O -) 2 -OH O = P (O -) 3, HO - [P (O) (O -)] w -P (O) (O -) 2 ( here, w is an integer); xiv) acetate; xv) a triplet; And xvi) borates, such as tetrafluoroborate; And xvii) sulfate S (O) ₂ O ₂ ^- or SO ₄ ^2- and hydrogensulfate HSO ₄ ^- ;

Anionic counterions derived from organic or inorganic acid salts ensure the electrical neutrality of the molecule; Thus, when an anion contains several anionic charges, the same anion can provide for the electrical neutrality of several cationic groups in the same molecule, or else it can provide for the electrical neutrality of several molecules ≪ / RTI > For example, a dye containing a group of two cationic two "charged in a single" anionic counterion or a "double charged" anionic counterion, e.g., (O =) ₂ S ( O ^-) _2, or O = P (O ^-) may contain ₂ -OH;

In particular, the anionic counterion may be a halide, such as chloride, bromide, fluoride, or iodide; Hydroxides; Sulfate; Hydrogensulfate; Linear or branched C ₁ -C ₆ alkyl sulfates, such as methyl sulfate or ethyl sulfate ions; Carbonates and hydrogen carbonates; Carboxylic acid salts such as formate, acetate, citrate, tartrate and oxalate; Linear or branched C ₁ -C ₆ alkyl sulfonates, for example, methyl sulfonate ions; Aryl moieties, preferably arylsulfonates wherein the phenyl is optionally substituted with one or more C ₁ -C ₄ alkyl radicals, for example, 4-tolylsulfonate; Alkylsulfonyl, such as mesylate;

The term " chemical oxidant " means any oxidant other than atmospheric oxygen as is commonly used in the art. Thus, mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromate, persalt such as perborate and persulfate, and also enzymes, among which are peroxidases, 2-electron oxydorduducts Agases, such as, for example, quercetin, and 4-electron oxigenases, for example, lacca may be mentioned. Preferably, the chemical oxidizing agent is hydrogen peroxide.

Furthermore, the addition salts which can be used in the context of the present invention are, in particular, cosmetically acceptable bases, for example basifying agents as defined below, for example alkali metal hydroxides, Sodium hydroxide or potassium hydroxide, aqueous ammonia, addition salts with amine or alkanolamine;

The expression " at least one " is equivalent to " more than one & quot ;;

The limits of the numerical range are encompassed within such ranges, in particular, between the expressions " between " and " in ... ";

■ "inclusive" for a range of representation values means that the limits of such ranges are included in the defined range.

(a) Triarylmethane dye

The process and cosmetic composition for dyeing keratin fibers according to the present invention comprises (a) a compound of formula (I) as defined above, an optical isomer thereof, a geometric isomer thereof, a tautomer thereof, an organic or inorganic acid or base salt thereof, Or solvates thereof, e. G., Hydrates, and mixtures thereof. ≪ / RTI >

In particular, the dye of formula (I) is blue, purple or green and is dull and chromatic.

Preferably, R ₁ , R ₂ , R ' ₁ and R' ₂ , which may be the same or different,

- a hydrogen atom,

- linear or branched optionally substituted and / or optionally interrupted by one or more heteroatoms selected from oxygen and sulfur and / or by oxygen, sulfur, C (O), SO, SO ₂ and SO ₃ ^- A linear or branched C ₁ to C ₆ alkyl radical, preferably an unsubstituted linear or branched C ₁ to C ₆ alkyl radical, and a more preferentially unsubstituted linear or branched C ₁ to C ₄ alkyl radical,

- SO ₃ ^- group.

Preferably, n and m may be the same or different and represent two integers ranging from 0 to 2. According to a particular embodiment, n and m are the same and are zero.

Preferably, R < ₅ > is

- a hydrogen atom,

- SO ₃ ^- group, or

- it represents a radical -NR ₆ R _7, where, R ₆ and R ₇ may be the same or different and independently of one another, a hydrogen atom or a linear or branched C ₁ to C ₆ alkyl radical, and preferably, C ₁ to C ₄ alkyl radicals such as methyl or ethyl radicals.

(I) of the present invention, an optical isomer thereof, a geometric isomer thereof, a tautomer thereof, an organic or inorganic acid or base salt thereof, a solvate thereof, such as a hydrate thereof, and a mixture thereof (S) may be cationic, anionic or nonionic.

According to a particular embodiment of the invention, the triarylmethane dye (s) is selected from compounds of formula (I-cat) which are cationic (i. E. This includes the ammonium group on the phenyl group A) And an anion An ^- as defined above to counteract the cationic charge.

Other variants that will include radicals containing sulfate radical SO ^3- onto one of the dye (s) the ring A, B or C of formula (I-cat), in such a case, the dye of formula (I) anion an ^- does not include a sulfonate of correcting (Etsu beater dye) or a cation M ^+, e to the cationic charge of the ammonium.

[Formula I-cat]

In the above formula (I-cat)

It is understood that R ₁ to R ₅ , and R ' ₁ to R' ₃ , m, n and q are as defined above, and (I-cat) does not contain more than one sulfonate group.

According to another particular embodiment of the present invention, the triarylmethane dye (s) is anionic (i.e., it has an ammonium group attached to phenyl A and at least two sulfonate groups SO ³ on ring A, ^- , which does not contain an ammonium group on the A-phase and does not contain at least one sulfonate group SO ^{3 -} on one of the rings A, B or C) (I-an "), wherein the dye then comprises at least one cation M ^< ⁺ > as previously defined to cancel out the anionic charge (s)

[Formula I-an '

[Chemical Formula I-an "]

In the formula (I-an ') or the formula (I-an "),

R ₁ to R ₅ , and R ' ₁ to R' ₃ , m, n and q are as defined below;

- (I-an ') comprises at least two sulfonate groups on ring A, B or C,

- (I-an ") comprises at least one sulfonate group on ring A, B or C,

At least one cation (s) M ⁺ as defined above is present to compensate for the anionic charge (s) of the sulfonate group (s).

According to certain other embodiments of the present invention, a triarylmethane dye (s) is a non-ionic (that is, such a thing does not contain an ammonium attached to the phenyl A or sulfonate group SO ^3-), the formula (I -nion): < / RTI >

[I-nion]

In the above formula (I-nion)

R ₁ to R ₅ and R ' ₁ to R' ₃ , m, n and q are as defined below, and (I-nion) does not contain any sulfonate groups on the ring A, .

According to a particular embodiment of the present invention, An ^- represents an anion selected from halide ions, for example bromide or chloride, methyl sulfate, toluene sulfonate or a mixture of such ions, and more preferentially, An ^- represents chloride .

According to a particular embodiment of the present invention, M ⁺ is selected from sodium, potassium, magnesium and calcium, preferably potassium.

According to a third particular embodiment of the invention, the dye (s) of formula (I) comprise at least one solvate and are preferentially selected from hydrochloride and phosphonate.

Preferably, the triarylmethane dye (s) is selected from the following compounds, optical isomers thereof, geometric isomers thereof, tautomers thereof, organic or inorganic acid or base salts thereof, solvates thereof, such as hydrates, Selected:

Y is as defined above.

More preferably, the triarylmethane dye (s) is selected from the following compounds 1a to 14a , optical isomers thereof, geometric isomers thereof, tautomers thereof, organic or inorganic acid or base salts thereof, solvates thereof, ≪ / RTI >

According to a first particular embodiment,

R ₁ , R ₂ , R ' ₁ and R' ₂ may be the same or different and independently of one another:

- a hydrogen atom,

Linear or branched C ₁ to C ₆ alkyl radicals, and more preferentially unsaturated, linear or branched C ₁ to C ₄ alkyl radicals such as methyl or ethyl radicals,

- SO ₃ ^- group;

N and m are the same and are 0;

Radicals R < ₄ > may be the same or different and, independently of one another,

A linear or branched C ₁ to C ₆ alkyl radical, preferably a linear or branched C ₁ to C ₄ alkyl radical, such as a methyl radical,

- hydroxyl radicals,

- SO ₃ ^- group,

- represents a halogen atom, preferably a chlorine atom,

Alternatively, two adjacent radicals R ₄ together form a benzo ring optionally substituted with an SO ₃ ^- group;

Q is an integer ranging from 0 to 4;

R ₅ is

- a hydrogen atom,

- SO ₃ ^- group,

- radical -NR ₆ R _{7 wherein} R ₆ and R ₇ , which may be identical or different, are, independently of each other, a linear or branched C ₁ to C ₆ alkyl radical and preferably a C ₁ to C ₄ alkyl radical, For example, methyl or ethyl radical.

According to a second particular embodiment,

R ₁ , R ₂ , R ' ₁ and R' ₂ may be the same or different and independently of one another:

- a hydrogen atom,

Linear or branched C ₁ to C ₆ alkyl radicals, and more preferentially unsubstituted, linear or branched C ₁ to C ₄ alkyl radicals such as methyl or ethyl radicals,

- SO ₃ ^- group;

N and m may be the same or different and are 1 or 2;

R ₃ and R ' ₃ may be the same or different and independently of one another:

A linear or branched C ₁ to C ₄ alkyl radical, preferably a methyl radical,

- SO ₃ ^- group,

Radicals R < ₄ > may be the same or different and independently of one another:

Linear or branched C ₁ to C ₆ , preferably linear or branched C ₁ to C ₄ , alkyl radicals such as methyl radicals,

- SO ₃ ^- group,

A halogen atom, preferably a chlorine atom,

Q is an integer of 1 or 2;

R ₅ is

- a hydrogen atom,

- SO ₃ ^- group,

- a radical -NR ₆ R ₇ (wherein, R ₆ and R ₇ may be the same or different and independently of one another, a hydrogen atom or a linear or branched C ₁ to C ₆ alkyl radical, and preferably, C ₁ to C ₄ alkyl radical, e. G., Methyl or ethyl radical).

Preferably, the triarylmethane dye (s) is selected from compounds 1 to 15, optical isomers thereof, geometric isomers thereof, tautomers thereof, organic or inorganic acid or base salts thereof, solvates thereof, For example, hydrates, and mixtures thereof; And, more preferably, as defined above, the compounds 1a to 14a, the optical isomers thereof, the geometric isomers thereof, the tautomers thereof, the organic or inorganic acid or base salts thereof, the solvates thereof, ≪ / RTI >

(b) Fluorescent dye

The process and composition for dyeing keratin fibers according to the present invention may also comprise (b) at least one fluorescent dye, wherein the fluorescent dye is selected from the group consisting of a cyanine dye, a styryl / hemicyanine dye, a naphthalimide dye, And mixtures thereof.

More specifically, the fluorescent dye (s) of the present invention are different from fluorescent dyes containing disulfide bonds. More preferably, the fluorescent dye (s) of the present invention do not contain a bond containing the same adjacent heteroatom as a direct dye.

In addition, fluorescent dyes described in EP 1 133 975, WO 03/029 359, EP 860 636, WO 95/01772, WO 95/15144, EP 714 954, and encyclopaedia The chemistry of synthetic dyes by K. Venkataraman, 1952, Academic Press, vol. 1 to 7, in Kirk Othmer's encyclopaedia Chemical Technology , in the chapter "Dyes and Dye Intermediates", 1993, Wiley and Sons, and various chapters of Ullmann's Encyclopedia of Industrial Chemistry 7th edition, Wiley and Sons, especially in Ullmann's Encyclopedia of Industrial Chemistry in the chapter "Fluorecent Dyes ", 2005, Wiley-VCH Verlag GmbH & KGaA, Weinheim 10.1002 / 143560007.a11_279; in the Handbook - A Guide to Fluorescent Probes and Labeling Technologies , 10th Ed. Molecular Probes / Invitrogen-Oregon 2005, published on the Internet or in previously printed versions] can be mentioned.

Preferably, the fluorescent dye (s) of the present invention is cationic.

More preferably, the fluorescent dye is a direct dye and is cationic, and more preferably, the fluorescent dye (s) (b) is selected from styryl or hemicyanine cation dyes.

More preferably, the fluorescent dyes of the present invention absorbs the absorption wavelength λ _abs of the light in the yellow, orange, and red range of the light, preferably, 400 nm to 500 nm (inclusive).

According to one variant, the fluorescent dye of the invention contains at least one cationic radical which is generated by or contained by at least one of the fluorescent chromophores.

Preferably, the cationic radical is quaternary ammonium; More preferably, the cationic charge is endocyclic.

Such cationic radicals are, for example,

- a cationic radical with an outward ring (di / tree) (C ₁ -C ₈ ) alkylammonium charge,

- cationic radicals having an inward ring charge, such as the following cationic heteroaryl groups: acridinium, benzimidazolium, benzo bistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazole Wherein the compound is selected from the group consisting of zwitterion, zwitterion, benzotriazolium, benzoxazolium, bi pyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphtoimidazolium, , Naphthopyranosol, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenoxazolium, pyrazinium, pyrazolium, pyrazolyltriazolium, pyridinium, pyridinoimidazolium, Thiazolium, triazolium, thiazolium, thiazolopyridinium, thiazolylimidazolium, thiopyrilium, triazolium, or zantilium.

According to a preferred variant of the invention, the fluorescent dyes of the present invention comprise at least one quaternary ammonium radical, such as a polymethine chromophore, having at least one cationic chromophore and selected from the following formulas (III) and (IV) Includes:

(III)

(IV)

In the above formulas (III) and (IV)

W ⁺ particularly represents a cationic heteroaryl group, especially including quaternary ammonium optionally substituted with one or more (C ₁ -C ₈ ) alkyl groups optionally substituted with one or more hydroxyl groups;

W & apos ^{; +} represents a divalent heteroaryl radical as defined for W ^{& lt; + &} gt ;;

Ar is an aryl group such as phenyl or naphthyl, preferably i) one or more halogen atoms such as chlorine or fluorine; ii) one or more (C ₁ -C ₈₎ alkyl, preferably, C ₁ -C _4, for alkyl groups such as methyl; iii) one or more hydroxyl groups; iv) one or more (C ₁ -C ₈ ) alkoxy groups, for example methoxy; v) one or more hydroxy (C ₁ -C ₈ ) alkyl groups such as hydroxyethyl, vi) one or more amino or (di) (C ₁ -C ₈ ) alkylamino groups, A C ₁ -C ₄ alkyl moiety optionally substituted with a hydroxyl group, for example, (di) hydroxyethylamino, vii) one or more acylamino groups; viii) optionally substituted with one or more heterocycloalkyl groups such as piperazinyl, piperidyl or 5-or 6-membered heteroaryl, such as pyrrolidinyl, pyridyl and imidazolinyl, An aryl group such as phenyl or naphthyl;

Ar ' is a divalent aryl radical as defined for Ar;

M 'represents an integer of 1 to 4 (inclusive of the boundary value), in particular, m' is 1 or 2, more preferably 1;

R ^c and R ^d may be the same or different and represent a hydrogen atom or an optionally substituted (C ₁ -C ₈ ) alkyl and preferably a C ₁ -C ₄ alkyl group or, alternatively, R ^c Is adjacent to W or W 'and / or R ^d is adjacent to Ar or Ar' and forms, together with the atom (s) thereof, (hetero) cycloalkyl, especially R ^c is adjacent to W ⁺ or W ' ⁺ And forms a (hetero) cycloalkyl, such as cyclohexyl;

Q ^- is an organic or inorganic anionic counterion;

(*) Represents the portion of the fluorescent chromophore bound to the remainder of the dye.

Preferably W ⁺ or W & apos ^{; +} is selected from the group consisting of imidazolium, pyridinium, benzimidazolium, pyrazolium, benzothiazolium or quinolinium, optionally substituted by one or more same or different C ₁ -C ₄ alkyl radicals Radical.

According to a particularly preferred embodiment of the invention, the fluorescent chromophore (s) of the dye (III) or the dye (IV) are those wherein m 'is 1 and Ar is a styryl group -C (R ^d ) = C (R ^c ) para to the (di) (hydroxy) (C ₁ -C ₆₎ (alkyl) amino group, for example, dihydroxy (C ₁ -C ₄₎ alkylamino represents a group is substituted phenyl, W 'for the ⁺ Is an imidazolium or pyridinium group, preferentially ortho- or para-pyridinium.

According to another preferred variant of the invention, the fluorescent chromophore (s) of the dye is cationic and comprises at least one quaternary ammonium radical, for example a cationic outward ring charge of the formula (IIIa) or (IVa) Zinc napthymidyl includes:

≪ RTI ID = 0.0 &

또는

or

(IVa)

는 염료와의 결합을 나타내며,here,

Represents a bond with a dye,

In the above formulas (IIIa) and (IVa), R ^e , R ^f , R ^g and R ^h may be the same or different and each represents a hydrogen atom or preferentially a di (C ₁ -C ₆ ) tree (C ₁ -C ₆₎ alkylammonium group, for example, represents an optionally substituted (C ₁ -C ₆₎ alkyl ammonium.

According to a particular embodiment, the fluorescent dye (s) (b) of the present invention is a compound of the formula (V), (VI) or (VII) and also its organic or inorganic acid or base salt, its optical isomer, Geometric isomers and tautomers thereof, and solvates thereof, for example, hydrates thereof:

(V)

(VI)

(VII)

In the formulas (V), (VI) and (VII)

R ₁ and R ₂ , which may be the same or different, each represent a hydrogen atom or a C ₁ -C ₆ alkyl group; Preferentially represents a hydrogen atom;

G ₁ represents a hydrogen atom or a group selected from NH ₂ and OH;

R _a , R ' _a , R " _a , R" _a , R _b , R' _b , R " _b and R "_'b may be the same or different, a) from the group of a hydrogen atom, b) a halogen atom, to groups: c) _{amino, d) (C 1 -C 4} ) alkylamino, e) (C ₁ - C ₄₎ dialkylamino, f) cyano, g) carboxyl -C (O) OH or the carboxylate ^{-C (O) O -, Q} +, h) hydroxyl -OH or alkoxide -O ^- Q ⁺ , i), (poly) halo (C ₁ -C ₆₎ alkyl, e.g., trifluoromethyl, j) acylamino, k) (C ₁ -C ₆₎ alkoxy, l) (C ₁ -C ₆₎ alkylthio, m) (poly) hydroxy (C ₂ -C _{4) alkoxy, n) (C 1 -C 6} ) _{alkylcarbonyloxy, o) (C 1 -C 6} ) alkoxycarbonyl, p) (C ₁ -C ₆₎ alkylcarbonylamino, q) acylamino, r) _{carbamoyl, s) (C 1 -C 6} ) alkyl-sulfonylamino, t) aminosulfonyl, u) -SO ₃ H or sulfonate -SO ₃ ^- a, Q ^+, or v) (C ₁ -C ₆₎ a group selected from alkoxy, hydroxyl, cyano, carboxyl, amino, (di) (C ₁ -C ₄₎ alkylamino, optionally substituted ( C ₁ -C ₆ ) alkyl, Alternatively, two alkyl radicals having a nitrogen atom of the amino group form a 5- to 7-membered heterocycle optionally containing another nitrogen or non-nitrogen heteroatom; in particular, R _a , R ' _a , R _"a, R"_'a, R _b, R' _b, R _"b and R"_'b is hydrogen or halogen atom or a (C ₁ -C ₄₎ alkyl group, preferably, a hydrogen atom or represents ;

● Alternatively, the two groups on two adjacent carbon atoms, R _a and R _'a; R _b and R ' _b together form a benzo or indeno ring, a fused heterocycloalkyl or a fused heteroaryl group; Benzo, indeno, heterocycloalkyl or heteroaryl ring may be optionally substituted with one or more substituents selected from the group consisting of halogen atoms, amino, (C ₁ -C ₄ ) alkylamino, (C ₁ -C ₄ ) dialkylamino, nitro, cyano, methyl group, an acylamino trifluoromethyl, (C ₁ -C ₄₎ alkoxy (poly) hydroxy (C ₁ -C ₄₎ alkoxy, (C ₁ -C ₄₎ alkylcarbonyloxy, (C ₁ -C ₄₎ Alkoxycarbonyl or (C ₁ -C ₄ ) alkylcarbonylamino radical, an acylamino, a carbamoyl or alkoxyalkylsulfonylamino radical, an aminosulfonyl radical, or (C ₁ -C ₆ ) alkoxy, hydroxyl, (C ₁ -C ₆ ) alkyl radical optionally substituted by halogen, cyano, carboxyl, amino, (C ₁ -C ₄ ) alkylamino and (C ₁ -C ₄ ) dialkylamino, or alternatively , The two alkyl radicals in the nitrogen atom of the amino group may be replaced by a 5 to 7 membered heteroaromatic ring optionally containing another nitrogen or non- And forming a cycle; First, R _a and R ' _a together form a benzo group;

● Alternatively, the two groups R _i and R _a; And / or the groups R ' _i and R ≈ _a together form (fused) fused cycloalkyl, preferentially cycloalkyl, for example, cyclohexyl;

R _g represents a hydrogen atom, an optionally substituted (hetero) aryl (C ₁ -C ₄ ) alkyl group or a (C ₁ -C ₆ ) alkyl group; Preferentially, R _b represents a hydrogen atom or a (C ₁ -C ₃ ) alkyl or benzyl group;

R _e represents a covalent, linear or branched, optionally substituted (C ₁ -C ₈ ) alkylene or (C ₂ -C ₈ ) alkenylene hydrocarbon-based chain, preferably R _e is Unsubstituted (C ₁ -C ₆ ) alkylene;

● R _f is a hydrogen atom, (C ₁ -C ₄₎ alkoxy group, an amino group R ₃ R ₄ N-, ₄ quaternary ammonium groups _{M ', R 3 R 4 R} 5 N + - represents the, here, R _3, R ₄ and R ₅ may be the same or different and represent a (C ₁ -C ₄ ) alkyl group, or R ₃ R ₄ N- is an optionally substituted heteroaryl group, preferentially an optionally substituted imidazolyl Or alternatively M ', R ₃ R ₄ R ₅ N ⁺ - represents an optionally substituted cationic heteroaryl group, preferentially imidazolyl optionally substituted with a (C ₁ -C ₃ ) alkyl group, Lt; / RTI >

G is an i) group -NR _c R _d , ii) -OR where R is a) a hydrogen atom, b) an optionally substituted, preferentially unsubstituted (C ₁ -C ₆ ) alkyl group, c ) optionally substituted (hetero) aryl group, d) an optionally substituted (hetero) aryl (C ₁ -C ₆₎ alkyl group, e.g., benzyl, e) an optionally substituted (hetero) cycloalkyl, f (C ₁ -C ₆ ) alkyl), according to certain embodiments, G represents a group -NR _c R _d , and according to other particular embodiments, G represents (C ₁ -C _6), or represent an alkoxy group;

Alternatively, when G represents -NR _c R _d , the two groups R _c and R ' _a and / or R _d and R _a together comprise one or more (C ₁ -C ₆ ) alkyl groups, Form a 5-to 7-membered heterocyclo-substituted saturated heteroaryl or heterocycle containing one or two heteroatoms selected from oxygen, nitrogen and oxygen; More preferably, the heterocycle is selected from morpholinyl, piperazinyl, piperidyl and pyrrolidinyl groups;

R _c and R _d may be the same or different and are hydrogen atoms or a) optionally substituted (hetero) aryl such as phenyl, b) optionally substituted (hetero) aryl (C ₁ - c ₄₎ alkyl, c) an optionally substituted (hetero) cycloalkyl, d) an optionally substituted (hetero) cycloalkyl (c ₁ -C _{4) alkyl, f) (c 2 -C 5} ) alkyl, or g) an optionally substituted (C ₁ -C ₈₎ alkyl, preferably, hydroxyl, carboxyl, carboxylate, optionally substituted with sulfate or sulfonate, (C ₁ -C _8), or represents a group of alkyl;

Alternatively, two adjacent radicals R _c and R _d at the same nitrogen atom together form an optionally substituted heterocyclic or an optionally substituted heteroaryl group;

R _i and R ' _i may be the same or different and represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group;

은 페닐 고리에 융합된 (헤테로)아릴 기를 나타내거나, 대안적으로, 페닐로부터 부재하거나, 우선적으로, 고리가 존재할 때, 고리가 벤조이며;●

(Hetero) aryl group fused to a phenyl ring, or, alternatively, absent from the phenyl, or, preferentially, when the ring is present, the ring is benzo;

M is an integer from 1 to 18 inclusive, particularly an integer from 1 to 14 inclusive; Preferentially, an integer of 2 to 10 (including a boundary value); More preferably, an integer of 3 to 8; More specifically, an integer of 4 to 6;

M represents an anionic counterion derived from an organic or inorganic acid salt which assures electrical neutrality of the dye, or from an organic or inorganic base;

Q ⁺ represents a cationic counterion derived from an organic or mineral acid salt, or an organic or inorganic base, which ensures electrical neutrality of the dye, for example an alkali metal, an alkaline earth metal or ammonium;

It is understood that when the dye comprises a carboxylate, sulfonate or alkoxide group, M 'and Q ⁺ may not be present to ensure the electrical neutrality of the dye.

According to one embodiment, the fluorescent dye of the present invention is a compound of formula (V) as defined above.

According to a preferred embodiment, the fluorescent dye (s) of the present invention comprises a styryl dye of the formula (VIII), and also organic or inorganic acid or base salts thereof, optical isomers, geometric isomers and tautomers thereof, and solvates, For example, it is selected from hydrate:

(VIII)

In the general formula _{(VIII), G, G 1} , R a, R 'a, R "a, R b, R' b, R" b, R i, R 'i, R 1, R 2 and m are the general formula 0.0 > (V). ≪ / RTI >

In particular, the dye (s)

R ₁ and R ₂ may be the same or different and represent a hydrogen atom;

R _i and R ' _i may be the same or different and represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group, preferably hydrogen;

R _a , R ' _a and R " _a may be the same or different and each represents a hydrogen atom, a halogen atom such as fluorine, or -OH, -O ^- Q ⁺ , (C ₁ -C ₆ ) Nitro, or cyano group, Q ⁺ is as defined above;

R _b , R ' _b and R " _b may be the same or different and represent a hydrogen atom or a (C ₁ -C ₆ ) alkyl group;

● Alternatively, two adjacent radicals R _b and R _'b, together with the carbon atom having this that, to form a condensed or fused benzo groups pyridinium, wherein the benzo groups may be substituted, and; Preferably, said benzo group is unsubstituted;

G represents an optionally substituted, preferentially unsubstituted group -NR _c R _d or a (C ₁ -C ₆ ) alkoxy group; According to certain embodiments, G represents a group -NR _c R _d , according to another particular embodiment G represents a (C ₁ -C ₆ ) alkoxy group;

R _i and R ' _i , which may be the same or different, each represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group,

는 페닐 고리에 융합된 아릴 또는 헤테로아릴 기를 나타내거나; 대안적으로, 페닐 고리에서 존재하지 않고; 우선적으로, 고리가 존재할 때, 고리는 벤조이고;●

Represents an aryl or heteroaryl group fused to a phenyl ring; Alternatively, is not present at the phenyl ring; Preferentially, when a ring is present, the ring is benzo;

M represents an integer from 1 to 18 inclusive; In particular an integer from 2 to 16 (inclusive); Preferentially, an integer of 3 to 10; More preferably, an integer of 4 to 6;

R _c and R _d may be the same or different and represent a hydrogen atom, a (C ₂ -C ₄ ) alkyl group or a substituted (C ₁ -C ₈ ) alkyl group, _{, ii) (C 1 -C 3} ) alkoxy, iii) hydroxyl, and iv) (C ₁ -C ₃₎ by at least one group selected from an alkyl-carbonyl, preferably, substituted with one or more hydroxy (C ₂ - C ₄ ) alkyl;

M 'represents an anionic counterion derived from an organic or inorganic acid salt or from an organic or inorganic base which ensures the electrical neutrality of the dye;

When the dye comprises an alkoxide group, it is selected from compounds of the formula (VIII), which it is understood that M 'and Q ⁺ may not be present to ensure the electrical neutrality of the dye.

Preferably, the fluorescent dye (s) (b) of the present invention is a styryl dye of the formula (IX) and also an organic or inorganic acid or a base salt thereof, optical isomers, geometric isomers and tautomers thereof, Cargo, for example, hydrate:

(IX)

In the above formula (IX), G, G ₁ , R _a , R ' _a , R _b , R' _b and m are as defined above.

According to a particular embodiment, the group G is in the para position relative to the -CH = CH- group, i.e. at the position 4 'of the phenyl group. According to another particular embodiment, the group G is in ortho position with respect to the -CH = CH- group, i.e. at position 2 ' of the phenyl group. According to one embodiment, the -CH = CH- group is in the para position of the pyridinium group, i.e., at position 4.

According to another advantageous variant, the -CH = CH- group is in the ortho position of the pyridinium group, i.e. in position 2.

According to a preferred mode of the present invention, the fluorescent dye (s) (b) of the present invention are compounds of the following formula (X) and formula (XI), and also their organic or inorganic acid or base salts, their optical isomers, Tautomers, and solvates thereof, for example, hydrates thereof:

(X)

(XI)

In the above formulas (X) and (XI)

R ¹ , R ² , R ³ and R ⁴ may be the same or different and represent a hydrogen atom or a (C ₁ -C ₆ ) alkyl group; Preferably, R ² and R ³ represent a hydrogen atom, R ¹ and R ⁴ may be the same or different and represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group;

^{● R 5, R 6, R} 7, R 8 and R ⁹ are, may be the same or different, i) hydrogen atom or ii) a halogen atom, e.g., Cl, Br or F, iii) group OR (where , R is a group of from ⁺ Q, or (C ₁ -C ₃₎ represents an alkyl group), to groups such as those described in the hydrogen atom or iv) aryl, for example, benzene, v) aryl (C ₁ - C ₃₎ alkyl, e.g., benzyl, vi) cyano, vii) _{nitro, viii) (C 1 -C 3} ) alkylthio, ix) amino NR ¹⁰ R ¹¹ (wherein, R ¹⁰ and R ¹¹ are the same or (A) a hydrogen atom, b) a (C ₂ -C ₄ ) alkyl group or c) a substituted (C ₁ -C ₈ ) alkyl group, preferably one or more groups selected from the following groups (C ₂ -C ₄ ) alkyl:

- cyano,

- (C ₁ -C ₃₎ alkoxy,

-Hydroxyl, and

- alkyl-carbonyl (C ₁ -C _3);

In particular, R ¹⁰ and R ¹¹ may be the same or different and are each a hydrogen atom or a (C ₁ -C ₆ ) alkyl group substituted by one or more hydroxyl, cyano or (C ₁ -C ₃ ) alkylcarbonyl groups, For example, hydroxyethyl;

M is an integer from 1 to 18 inclusive; In particular an integer from 2 to 16 (inclusive); Preferentially, an integer of 3 to 10; More preferably, an integer of 4 to 6;

M 'represents an anionic counterion as defined above;

It is understood that when the dye comprises an alkoxide group, M 'and Q ⁺ may not be present to ensure the electrical neutrality of the dye.

According to a first embodiment of the invention, the fluorescent dye (s) (b) comprises a compound of formula (X) having the following substituents, and also organic or inorganic acid or base salts, optical isomers, geometric isomers and tautomers, And solvates thereof, for example, hydrates thereof:

According to a second embodiment, the fluorescent dye (s) (b) is a compound of formula (XI) having the following substituents, and also organic or inorganic acid or base salts thereof, optical isomers, geometric isomers and tautomers thereof, A cargo, for example, is a luggage:

Preferably, the fluorescent dye (s) (b) is selected from compounds of the formulas (X ') and (XI'):

[Formula X '

(XI ')

In the above formulas (X ') and (XI'), R ⁵ , R ⁷ , R ⁸ and m are as defined above for the formulas (X) and (XI)

R ⁵ and R ⁸ , which may be the same or different, represent a hydrogen atom or a (C ₁ -C ₄ ) alkoxy group such as methoxy;

R ⁷ represents a (C ₁ -C ₄ ) alkoxy group or NR ¹⁰ R ¹¹ wherein R ¹⁰ is a hydrogen atom or b) i) cyano, ii) (C ₁ -C ₃ ) alkoxy, iii) hydroxyl groups, and iv) (C ₁ -C ₃₎ represents a group substituted with one or more groups selected from alkyl-carbonyl (C ₁ -C ₆₎ alkyl, R ¹¹ is a) i) cyano, ii) (C ₁ (C ₁ -C ₆ ) alkyl group substituted with one or more groups selected from (i) C ₃ ) alkoxy, (iii) hydroxyl and (iv) (C ₁ -C ₃ ) alkylcarbonyl;

In particular, NR ¹⁰ R ¹¹ is (C ₂ -C ₄₎ alkyl group, a (di) hydroxy (C ₂ -C ₄₎ alkylamino or hydroxy (C ₂ -C ₄₎ alkyl ((C ₁ -C ₄₎ Alkyl) amino group;

M is an integer from 1 to 18 inclusive; In particular an integer from 2 to 16 (inclusive); Preferentially, an integer of 3 to 10; More preferably, an integer of 4 to 6;

M represents an anionic counterion derived from an organic or mineral acid salt or from an organic or inorganic base which ensures the electrical neutrality of the dye.

According to this embodiment, the fluorescent dye (s) (b) is preferably a compound of formula (X ') or (XI') having the following substituents and also organic or inorganic acid or base salts thereof, And tautomers, and solvates thereof, for example, hydrates.

According to another preferred mode of the present invention, the fluorescent dye (s) (b) of the present invention comprises a compound of the formula (XII) and a compound of the formula (XIII), and also an organic or inorganic acid or base salt thereof, , Geometric isomers and tautomers, and solvates thereof, for example, hydrates thereof:

(XII)

(XIII)

In the above formulas (XII) and (XIII)

R ¹ , R ² , R ³ and R ⁴ may be the same or different and represent a hydrogen atom or a (C ₁ -C ₆ ) alkyl group; Preferably, R ² and R ³ represent a hydrogen atom, R ¹ and R ⁴ may be the same or different and represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group;

^{● R 5, R 6, R} 7, R 8 and R ⁹ may be the same or different, i) hydrogen atom or ii) a halogen atom, e.g., Cl, Br or F, iii) group OR (where, R represents a Q ⁺ as described in the hydrogen atom or the above), or (C ₁ -C ₃₎ alkyl group, a group from the groups to iv) aryl, for example, benzene, v) aryl (C ₁ - C ₃₎ alkyl, e.g., benzyl, vi) cyano, vii) _{nitro, viii) (C 1 -C 3} ) alkylthio, ix) represents an amino NR ¹⁰ R ^11, where, R ¹⁰ and R ¹¹ is A) a hydrogen atom or b) a (C ₁ -C ₈ ) alkyl group optionally substituted with one or more groups selected from the following groups:

- cyano,

- (C ₁ -C ₃₎ alkoxy,

-Hydroxyl, and

- alkyl-carbonyl (C ₁ -C _3);

In particular, R ¹⁰ and R ¹¹ may be the same or different and are each a hydrogen atom or one or more hydroxyl, cyano or (C ₁ -C ₃ ) alkylcarbonyl groups such as methyl, ethyl, butyl, iso butyl, cyano-ethyl, methyl-carbonyl, ethyl or optionally substituted with hydroxyethyl (C ₁ -C ₆₎ represents an alkyl;

M is an integer from 1 to 18 inclusive; In particular an integer from 2 to 16 (inclusive); Preferentially, an integer of 3 to 10; More preferably, an integer of 4 to 6;

M 'represents an anionic counterion derived from a salt of an organic or inorganic acid, preferably from Y;

It is understood that when the dye comprises an alkoxide group, M 'and Q ⁺ may not be present to ensure the electrical neutrality of the dye.

According to one embodiment of the present invention, the fluorescent dye (s) (b) comprises a compound of formula (XII), and also an organic or inorganic acid or base salt thereof, optical isomers, geometric isomers and tautomers thereof, For example, it is a hydrate:

According to another embodiment, the fluorescent dye (s) (b) comprises a compound of formula (XIII), and also organic or inorganic acid or base salts thereof, optical isomers, geometric isomers and tautomers thereof, and solvates thereof, to be:

More specifically, the fluorescent dye (s) (b) of the present invention is selected from compounds of the following formulas (XII ') and (XIII').

[Formula XII ']

[Formula XIII ']

In the above formulas (XII ') and (XIII'), R ⁵ , R ⁷ , R ⁸ and m are as defined above for formula (X) and formula (XI);

R ⁵ and R ⁸ , which may be the same or different, represent a hydrogen atom or a (C ₁ -C ₄ ) alkoxy group such as methoxy;

R ⁷ represents a (C ₁ -C ₄ ) alkoxy group or NR ¹⁰ R ¹¹ , wherein R ¹⁰ and R ¹¹ may be the same or different and are a) a hydrogen atom or b) i) cyano, ii (C ₁ -C ₈ ) alkyl optionally substituted with one or more groups selected from (C ₁ -C ₃ ) alkoxy, iii) hydroxyl, and iv) (C ₁ -C ₃ ) alkylcarbonyl; In particular, R ¹⁰ and R ¹¹ are hydrogen atoms, or (C ₁ -C ₆ ) alkyl groups which may be the same or different and are optionally substituted with one or more groups selected from the following groups: hydroxyl, cyano or ( C ₁ -C ₃ ) alkylcarbonyl, such as methyl, ethyl, butyl, isobutyl, cyanoethyl, methylcarbonylethyl or hydroxyethyl; Preferably, R ¹⁰ and R ¹¹ , which may be the same or different, represent a (C ₁ -C ₆ ) alkyl group, for example hydroxyethyl, optionally substituted by one or more hydroxyl groups;

M is an integer from 1 to 18 inclusive; In particular an integer from 2 to 16 (inclusive); Preferentially, an integer of 3 to 10; More preferably, an integer of 4 to 6;

M represents an anionic counterion derived from an organic or mineral acid salt or from an organic or inorganic base which ensures the electrical neutrality of the dye.

According to one embodiment, the fluorescent dye (s) (b) of the present invention is a compound of formula (XII ') or (XIII') having the following substituents, and also organic or inorganic acid or base salts thereof, its geometric isomers and tautomers Isomers, and solvates thereof, for example, hydrates thereof:

More specifically, the fluorescent dye (s) (b) of the present invention is selected from compounds of formula (V), formula (VIII) or formula (IX) as defined above wherein G represents a hydrogen atom.

More specifically, the fluorescent dye (s) (b) of the present invention is selected from compounds of the following formulas (XIV) and (XV):

(XIV)

(XV)

In the above formulas (XIV) and (XV), R ⁵ , R ⁷ , R ⁸ and m are as defined above for the formulas (X) and (XI)

R ⁵ and R ⁸ may be the same or different and each represents a hydrogen atom or a (C ₁ -C ₄ ) alkoxy group such as methoxy, preferably, R ⁵ and R ⁸ represent a hydrogen atom;

R ⁷ represents a (C ₁ -C ₄ ) alkoxy group or NR ¹⁰ R ¹¹ , wherein R ¹⁰ and R ¹¹ may be the same or different and are a) a hydrogen atom or b) i) hydroxyl, ii ) RZC (X) -Y- wherein X, Y and Z represent an oxygen or sulfur atom or N (R ') or alternatively, X and / or Z represent a bond and R and R' (Iii) sulfone SO ₃ H, iv) sulfonate SO ₃ ^- , Q ⁺ , or a salt thereof, wherein R _{1 and} R ₂ are the same or different and each represents a hydrogen atom or a (C ₁ -C ₆ ) alkyl group, v) carboxylate, ^{C (O) O -, Q} + ( wherein, Q ⁺ is an optionally substituted by at least one group selected from represents a cationic counter ion, for example, alkali metal or alkaline earth metal) (C ₁ - C ₈₎ represents an alkyl; In particular, R ⁷ represents a group NR ¹⁰ R ¹¹ , wherein R ¹⁰ and R ¹¹ may be the same or different and are a) a hydrogen atom or b) i) hydroxyl, ii) carboxyl, iii) butyl, iv) sulfonamide, and v) optionally substituted by at least one group selected from sulfonate, (C ₁ -C ₆₎ represents an alkyl, more in particular, a) hydrogen, or b) i) hydroxyl, ii) carboxyl, and iii) represents an optionally substituted (C ₁ -C ₆₎ alkyl with one or more groups selected from carboxylate;

M is an integer from 1 to 18 inclusive; In particular, an integer from 1 to 6 (inclusive); Preferentially, an integer of 1 to 4; More preferably, an integer of 1 to 2;

M 'represents an anionic counterion derived from an organic or inorganic acid salt or from an organic or inorganic base which ensures the electrical neutrality of the dye;

It is understood that when the dye comprises a sulfonate or carboxylate group, M 'and Q ⁺ may not be present to ensure the electrical neutrality of the dye.

More preferably, the fluorescent dye (s) (b) of the present invention is selected from the following compounds, their geometric isomers, tautomers thereof, solvates thereof and mixtures thereof:

In the above formula, M 'and Q ⁺ are defined above.

Oxidant

The process and cosmetic composition for dyeing keratin fibers according to the present invention may also selectively use or include one or more oxidizing agents.

Preferably, the oxidant (s) are selected from chemical oxidants.

The term "chemical oxidant" means an oxidant other than atmospheric oxygen.

More specifically, the chemical oxidant (s) can be selected from the group consisting of hydrogen peroxide, hydrogen peroxide-generating systems, urea peroxides, alkali metal bromates or pericyanides, peroxidated salts such as persulfates, perborates, peracids and their precursors and alkali Percarbonates of metals or alkaline earth metals, and mixtures thereof.

Preferably, the chemical oxidant (s) are selected from hydrogen peroxide and hydrogen peroxide-generating systems.

According to a preferred embodiment, the hydrogen peroxide-generating system (s) comprise urea peroxide, polyvinylpyrrolidone / H ₂ O ₂ ; Oxydase; Perborate; And a polymer complex capable of releasing hydrogen peroxide selected from percarbonate.

Preferably, the chemical oxidizing agent is hydrogen peroxide, and, more preferably, an aqueous hydrogen peroxide solution.

The chemical oxidant (s) are advantageously applied in the form of an aqueous solution wherein the content of oxidizing agent is preferably from 0.05% to 5% by weight, and more preferably from 0.1% to 2% by weight, based on the total weight of the aqueous solution.

According to a preferred embodiment of the present invention, the dyeing process does not use any oxidizing agent.

According to this preferred embodiment of the present invention, the cosmetic composition comprising the component (a) and the component (b) does not contain any oxidizing agent.

reducing agent

The process and cosmetic composition for dyeing keratin fibers according to the present invention may also selectively use or include one or more reducing agents.

The reducing agent (s) useful in the present invention is advantageously selected from compounds of formula (XVI), and also addition salts thereof and mixtures thereof:

(XVI)

In the above formula (XVI):

X represents P, S or SO ₂ ,

- q represents an integer of 0 or 1,

- t represents an integer of 1 or 2,

R is optionally interrupted by a heteroatom and / or is selected from the group consisting of hydroxyl, halo, amine, carboxyl, ((C ₁ -C ₃₀ ) alkoxy) carbonyl, amido, ((C ₁ -C ₃₀ ) Linear or branched, saturated or unsaturated C ₁ to C ₆ alkyl optionally substituted with one or more radicals selected from the group consisting of (C ₁ -C ₃₀ ) acyl) amino, mono or dialkylamino, and mono- or dihydroxylamino radicals. C ₂₀ represents an alkyl radical.

Preferably, the reducing agent (s) is selected from the group consisting of thioglycolic acid, thiolactic acid, glyceryl monothioglycolate, cysteamine, N-acetyl cysteamine, N-propionyl cysteamine, cysteine, N- (Mercaptoalkyl) -? - hydroxyalkylamide, N-mono- or N, N-dialkylmercapto-4-butyramide, aminomercapto Alkyl amides, N- (mercaptoalkyl) succinic acid and N- (mercaptoalkyl) succinimide derivatives, alkylaminomercaptoalkylamides, 2-hydroxypropyl thioglycinate and (2-hydroxy- ) Ethyl thioglycolate, mercaptoalkylaminoamides, N-mercaptoalkylalkanediamides and formamidinesulfonic acid derivatives, salts thereof, and mixtures thereof.

Preferably, the reducing agent (s) is also selected from a salt, e. G. Sodium sulfite, sodium dithionite or sodium thiosulfate, and mixtures thereof.

The chemical reducing agent (s) are advantageously applied in the form of an aqueous solution wherein the content of chemical reducing agent is from 0.01% to 10% by weight, and more preferably from 0.1% to 5% by weight, based on the total weight of the aqueous solution.

According to a preferred embodiment of the present invention, the dyeing process does not use any reducing agent.

According to this preferred embodiment of the present invention, the cosmetic composition comprising the component (a) and the component (b) does not contain any reducing agent.

Cosmetics media and solvents

(A) triarylmethane dye (s) selected from compounds of formula (I) as defined above, and (b) fluorescent dye (s) as defined above, and also, if present, ) And / or the reducing agent (s) may be dissolved in advance prior to application to the keratinous fibers.

In other words, the components used in the dyeing process of the present invention may be present in one or more compositions.

The composition (s) comprising the constituents according to the invention are a cosmetic composition, i. E. These are preferably aqueous. In addition to water, these may include one or more organic solvents, or mixtures thereof.

Examples of organic solvents that may be mentioned include linear or branched C ₂ to C ₄ alkanols, such as ethanol and isopropanol; Glycerol; Polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, hexylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and also aromatic alcohols or ethers, For example, benzyl alcohol or phenoxyethanol, and mixtures thereof.

pH

The pH of the composition of the present invention comprising composition (a) and component (b) used in the dyeing process of the present invention is preferably between 2 and 12, and more preferably between 3 and 11 to be. This can be adjusted using acidifying or basifying agents commonly used in dyeing keratin fibers, or alternatively, to the desired values using standard buffer systems.

The pH of the composition comprising component (a) and component (b), and the pH of the composition (s) used in the dyeing process of the present invention, is preferably between 6 and 11, inclusive, , 7 to 10, and even more preferably 7.5 to 9.5, such as 9 to 9.5.

Among the acidifying agents, inorganic and organic acids as defined above, mention may be made, as examples, of inorganic or organic acids such as hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, , And sulfonic acid.

The alkaline agent (s) may in particular be selected from inorganic, organic or hybrid alkalizing agents, and mixtures thereof.

The inorganic alkaline agent (s) are preferably selected from the group consisting of ammonia, alkaline carbonates or bicarbonates such as ammonium, sodium or potassium carbonate or bicarbonate, ammonium, sodium or potassium hydroxide, Or a mixture thereof.

The organic alkaline agent (s) are preferably selected from organic amines having a pK _b of less than 12, preferably less than 10, and more advantageously less than 6 at 25 ° C. It should be noted that this is related to the pK _b corresponding to the function with the highest basicity. Also, the organic amine does not include any alkyl or alkenyl fat chain containing more than 10 carbon atoms.

The organic alkaline agent (s) are preferably selected from the group consisting of alkanolamines, especially mono-, di- or tri-hydroxy (C ₁ -C ₆ ) alkylamines, such as triethanolamine, oxyethylenated and / Or oxypropylenated ethylenediamine, an amino acid, a polyamine of formula (XVII), and mixtures thereof.

(XVII)

In the general formula (XVII), W is one or more hydroxyl groups or C ₁ -C ₆ being optionally substituted by alkyl radicals and / or one or more hetero atoms, for example, optionally interrupted by O, or -NR _u 2 Is a C ₁ -C ₆ alkylene radical; R _x , R _y , R _z , R _t and R _u may be the same or different and are a hydrogen atom or a C ₁ -C ₆ alkyl, a C ₁ -C ₆ hydroxyalkyl or a C ₁ -C ₆ aminoalkyl radical .

Examples of amines of formula (XVII) which may be mentioned include 1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine.

The term "alkanolamine" is intended to mean an organic amine comprising a primary, secondary or tertiary amine functional group, and at least one linear or branched C ₁ to C ₈ alkyl group having at least one hydroxyl radical.

Organoamines selected from alkanolamines comprising one to three identical or different C ₁ to C ₄ hydroxyalkyl radicals, for example, monoalkanolamines, dialkanolamines or trialkanolamines, . ≪ / RTI >

Of these types of compounds, monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N, N-dimethylethanolamine, 2-amino- Amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol and tris (hydroxymethyl) aminomethane are preferred. Can be mentioned.

More specifically, the amino acid that can be used is an amino acid of natural or synthetic origin in its L, D, or racemic form, and more specifically, at least one acidic functional group selected from a carboxylic acid, a sulfonic acid, a phosphonic acid, . Amino acids may be in neutral or ionic form.

Examples of the amino acids which can be used in the present invention include aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, , Serine, taurine, threonine, tryptophan, tyrosine and valine.

Advantageously, the amino acid is a basic amino acid comprising an additional amine functional group optionally included in the ring or in the ureido functional group.

Such a basic amino acid is preferably selected from those corresponding to the formula (XVIII), and also salts thereof:

(XVIII)

In the above formula (XVIII), R is imidazolyl, preferably imidazolyl-4-yl; Aminopropyl; Aminoethyl; _{- (CH 2) 2 N (} H) -C (O) -NH 2; And - (CH ₂ ) ₂ -N (H) -C (NH) -NH ₂ .

Compounds corresponding to formula (XVIII) are histidine, lysine, arginine, ornithine and citrulline.

The organic amine may also be selected from organic amines of the heterocyclic type. In addition to the histidine already mentioned in the amino acid, in particular, pyridine, piperidine, imidazole, triazole, tetrazole, and benzimidazole can be mentioned.

The organic amine may also be selected from amino acid dipeptides. As amino acid dipeptides which can be used in the present invention, in particular, carnosine, anserine and valerin can be mentioned.

The organic amine may also be selected from compounds containing a guanidine functional group. As amines of this type that can be used in the present invention, mention may be made of, in addition to arginine already mentioned as an amino acid, in particular, creatine, creatine 1,1-dimethylguanidine, 1,1-diethylguanidine, glycoxyamine, metformin, aminodinoalanine, 3-guanidino propionic acid, 4-guanidinobutyric acid, and 2 - ([amino (imino) methyl] amino) ethane-1-sulfonic acid.

Hybrid compounds which may be mentioned include salts of the previously mentioned amines having an acid, such as, for example, carbonic acid or hydrochloric acid.

Guanidine carbonate or monoethanolamine hydrochloride may especially be used.

Preferably, the alkaline agent (s) useful in the present invention is selected from aqueous ammonia, alkanolamines, amino acids in neutral or ionic form, especially basic amino acids, and preferably corresponding to formula (XVIII).

More preferably, the alkaline agent (s) are selected from the group consisting of aqueous ammonia, ammonium bicarbonate, ammonium hydroxide, mono-, di- or tri-hydroxy (C ₁ -C ₆ ) alkylamines, such as triethanolamine , And mixtures thereof.

Form of composition

The composition (s) comprising the triarylmethane dye (s) (a) selected from the compounds of formula (I) as defined above and the fluorescent dye (s) (b) May have a presentation form, for example, a liquid, lotion, cream, or gel form, or any other form suitable for dyeing keratin fibers.

It may also be packaged under pressure in an aerosol container or in a non-aerosol container in the presence of a propellant and form a foam.

additive

When the constituents used in the dyeing process according to the present invention are present in one or more composition (s), the composition may also optionally include one or more additives different from the constituents of the present invention, , Fatty substances, cationic, anionic, nonionic, amphoteric or zwitterionic surfactants, cationic, anionic, nonionic, or ampholytic polymers, or mixtures thereof, anti-dandruff agents, anti- Sunscreen, inorganic or organic pigments, sequestering agents, plasticizers, solubilizing agents, acidifying agents, inorganic or organic thickeners, in particular polymer thickeners, such as, for example, preservatives and / or enhancing hair regrowth, , Milky or pearlescent agents, antioxidants, hydroxy acids, perfumes, preservatives, pigments and ceramides can be mentioned.

Needless to say, those skilled in the art will appreciate that the beneficial properties inherently related to the composition (s) according to the present invention are not adversely affected by, or largely affected by, the conceived additive (s) Will be carefully selected.

The additive may generally be present in each of these in an amount of from 0 to 20% by weight, based on the total weight of the composition comprising it.

Dyeing process

The step of dyeing the keratin fibers according to the present invention comprises the steps of:

(a) compounds of formula (I) as defined above, and also optical isomers, geometric isomers, tautomers, organic or inorganic acid or base salts thereof, solvates thereof, such as hydrates, and At least one triarylmethane dye selected from mixtures of

(b) the application of the constituents of one or more fluorescent dyes as defined above, wherein the triarylmethane dye (s) (component (a)) and the fluorescent dye (s) (component (b)) Are applied to the keratin fibers together or sequentially.

In other words, the dyeing process according to the invention can be carried out in one or more steps.

According to a particularly preferred embodiment, the triarylmethane dye (s) (a) and the fluorescent dye (s) (b), as defined above, are applied to the keratin fibers together (or jointly) . According to this embodiment, the dyeing process is carried out in one step.

According to this one-step embodiment, the process comprises adding to the keratin fiber a compound of formula (I) as defined above and its optical isomer, its geometric isomer, its tautomer, its organic or inorganic acid or base (B) according to the invention comprising at least one triarylmethane dye (a) selected from a salt, a solvate thereof, for example a hydrate, and mixtures thereof, and at least one fluorescent dye (b) And applying the composition.

According to another particularly preferred embodiment, the triarylmethane dye (s) (a) as defined above and the fluorescent dye (s) (b) as defined above are applied sequentially, i. E. Continuously . According to this alternative embodiment, the dyeing process is carried out in at least two stages.

According to a first embodiment of at least two stages, the fluorescent dye (s) (b) as defined above is applied to the keratin fibers and subsequently the triarylmethane dye (s) (a ) Is applied. In other words, the fluorescent dye (s) (b) as defined above is applied after the triarylmethane dye (s) (a) as defined above.

According to this first embodiment, the process of dyeing keratin fibers comprises at least the following two consecutive steps:

To said keratin fibers, a compound of formula (I) as defined above and its optical isomers, its geometric isomers, its tautomers, its organic or inorganic, acid or base salts, its solvates, A first step of applying a cosmetic composition comprising at least one triarylmethane dye (a) selected from the group consisting of hydrates, hydrates, and mixtures thereof,

- a second step of applying a cosmetic composition comprising one or more fluorescent dyes (b) as defined above to said keratin fibers.

According to a preferred embodiment of at least two steps, the triarylmethane dye (s) (a) as defined above is applied to the keratin fibers, and subsequently the fluorescent dye (s) (b) Is applied. In other words, the triarylmethane dye (s) (a) as defined above is applied after the fluorescent dye (s) (b) as defined above.

According to this preferred embodiment, the process of dyeing keratin fibers comprises at least the following two consecutive steps:

- a first step of applying a cosmetic composition comprising one or more fluorescent dyes (b) as defined above to said keratin fibers,

To said keratin fibers, a compound of formula (I) as defined above and its optical isomers, its geometric isomers, its tautomers, its organic or inorganic, acid or base salts, its solvates, A second step of applying a cosmetic composition comprising one or more triarylmethane dyes (a) selected from hydrates, hydrates, and mixtures thereof.

Preferably, the component (a) and the component (b) are applied to the keratin fibers at a bath ratio that can range from 0.1 to 10, and more specifically, from 0.2 to 8. For the purposes of the present invention, the term "bath ratio" means the ratio between the total weight of the component (a) or the component (b) and the total weight of the treated keratin fibers.

When the dyeing process is carried out in one step, the component (a) and the component (b) advantageously have a keratin content of from about 1 to about 90 minutes, and more preferably, from about 5 to about 60 minutes, It may be left on the fiber.

When the dyeing process is carried out in at least two stages, each of component (a) and component (b) is advantageously added for a period of time ranging from 1 minute to 60 minutes, and more preferentially from 5 to 45 minutes , And may remain on the keratin fibers.

At the end of the dyeing process according to the invention, in step 1 or at least step 2, the keratin fibers are advantageously washed with water. These can optionally be washed with shampoo, washed with water before being allowed to dry or dry.

When the dyeing process is carried out in at least two stages, the keratinous fibers are advantageously cleaned with water between each step. In other words, the dyeing process may include an intermediate cleaning step between the application of the first component and the application of the second component. During this intermediate cleaning step, the keratin fibers may optionally be washed with shampoo and subsequently washed with water before being allowed to dry or dry.

The dyeing process according to the present invention can be carried out at room temperature (25 DEG C) or while heating.

When these are present, the reducing agent (s) may be applied separately or together with one of the component (a) or the component (b). Preferably, when these are present, the reducing agent (s) is applied together with component (b).

When these are present, the oxidizing agent (s) may be applied separately or together with one of the component (a) or the component (b). Preferably, when these are present, the oxidizing agent (s) are applied after component (a) and component (b).

According to a particular embodiment, the process of dyeing keratin fibers according to the invention comprises the following successive steps:

To said keratin fibers, a compound of formula (I) as defined above and its optical isomers, its geometric isomers, its tautomers, its organic or inorganic, acid or base salts, its solvates, A first step of applying a cosmetic composition comprising at least one triarylmethane dye (a) selected from the group consisting of hydrates, hydrates, and mixtures thereof,

- a second step of applying to the keratin fiber at least one cosmetic composition comprising at least one fluorescent dye (b) as defined above and at least one reducing agent as defined above.

According to certain embodiments of the dyeing process of the present invention, no step of the process comprises an oxidizing agent.

According to another advantageous embodiment of the dyeing process of the present invention, no step of the process contains a reducing agent.

The dyeing process according to the invention can be applied to wet or dried, preferably dried, keratin fibers.

Multi-compartment device

The present invention also relates to the use of one or more triarylmethane dyes (a) selected from compounds of formula (I) as defined above and their optical isomers, their geometric isomers, their tautomers, their organic or inorganic acid or base salts , And a second compartment containing one or more fluorescent dyes (b) as defined above, as well as a first compartment containing a solvate thereof, for example a hydrate, and mixtures thereof, and a second compartment containing one or more fluorescent dyes will be.

Usage

The subject of the present invention is also the use of bright keratin fibers, in particular chertnut-brown, dark chestnut-brown, brown, shiny brown or even black human keratin fibers, without the use of additional dyes other than (a) (A) selected from compounds of formula (I) as defined above for dyeing hair, for example, for dyeing hair, as well as its optical isomers, its geometric isomers, its tautomers (B) as defined above, in combination with an organic or inorganic acid or base salt thereof, solvates thereof, e.g. hydrates, and mixtures thereof.

According to certain embodiments, "keratin fibers" are human keratin fibers, and more specifically, hairs.

The following examples serve to illustrate the present invention without intrinsically limiting it.

Example

In the following examples, all amounts are given as weight percentages relative to the total weight of the composition, unless otherwise specified.

I. First example of combined application

a) Preparation of the composition

The composition (A1) comprising the triarylmethane dye of formula (I) according to the invention is prepared from the ingredients mentioned in the table below.

The compositions (B1) and (B2) containing fluorescent dyes were prepared from the components mentioned in the table below.

b) Procedure

The compositions (A1), (B1) and (B2) obtained above were mixed to obtain the following mixtures:

- A1 / B1 ratio of 1/1, and

- 1/1 ratio of A1 + B2.

10 ml of compositions (A1), (B1), (B2), (A1 + B1) and (A1 + B2) were applied to 1 g of hair.

After a grace period of 20 minutes at room temperature, the hair was washed with water, squeezed and dried.

Thereafter, the hair was treated with ten shampoo washes consisting of two cycles of shampoo washing five times. After each shampoo wash cycle, the hair was dried and the hair color was measured using a Minolta CM2600d spectrophotometer (with reflective component, 10 ° angle, light source D65) in a CIEL ^* a ^* b ^* system.

In this system, L ^* denotes the intensity of the color, a ^* denotes the green / red color axis, and b ^* denotes the blue / yellow color axis.

The lower the L ^* value, the darker or more intense the color. The higher the a ^* value, the more red the hue is, and the higher the b ^* value, the hue becomes more yellowish.

c) Results

The results of coloring for hair containing 90% gray hair are provided in the table below.

The results obtained above show that the simultaneous application of the triarylmethane dye and the fluorescent dye of formula (I) according to the present invention is very intense and makes it possible to obtain a chromatic color.

These results also make it possible to obtain a brown color, in which the process according to the present invention, using only two specific direct dyes, triarylmethane dyes of formula (I) in combination with fluorescent dyes, is continued after 10 shampoo washes .

II. A second example of combined application

a) Preparation of the composition

The composition (A2) comprising the triarylmethane dye of the formula (I) according to the invention is prepared from the constituents mentioned in the table below.

The compositions (B3) and (B4), including fluorescent dyes, were prepared from the ingredients mentioned in the table below.

b) Procedure

The compositions (A2), (B3) and (B4) obtained above were mixed to obtain the following mixtures:

- 1/1 ratio A2 + B3, and

- A 1/1 ratio of A2 + B4.

10 ml of compositions (A2), (B3), (B4), (A2 + B3) and (A2 + B4) were applied to 1 g of hair.

After a grace period of 20 minutes at room temperature, the hair was washed with water, squeezed and dried.

Thereafter, the hair was treated with ten shampoo washes consisting of two cycles of shampoo washing five times. After each shampoo wash cycle, the hair was dried and the hair color was measured using a Minolta CM2600d spectrophotometer (with reflective component, 10 ° angle, light source D65) in a CIEL ^* a ^* b ^* system.

In this system, L ^* denotes the intensity of the color, a ^* denotes the green / red color axis, and b * denotes the blue / yellow color axis.

The lower the L ^* value, the darker or more intense the color. The higher the a ^* value, the more red the hue is, and the higher the b ^* value, the hue becomes more yellowish.

c) Results

The results of coloring for hair containing 90% gray hair are provided in the table below.

The results obtained above show that the simultaneous application of the triarylmethane dye and the fluorescent dye of formula (I) according to the present invention is very intense and makes it possible to obtain a chromatic color.

This result makes it possible to obtain a brown color, in which the process according to the invention, using only two specific direct dyes, namely triarylmethane dyes of formula (I) in combination with fluorescent dyes, lasts even after 10 shampoo washes .

III. Comparative Example

a) Preparation of the composition

The composition (A3) comprising the triarylmethane dye of formula (I) according to the invention is prepared from the components mentioned in the table below.

The composition (B5) containing a fluorescent dye as specified in the patent application EP 1 133 975 was prepared from the ingredients mentioned in the table below.

b) Procedure

The compositions (A3) and (B5) obtained above were mixed to obtain a 1/1 ratio mixture (A3 + B5).

10 ml of compositions (A3), (B5) and (A3 + B5) were applied to 1 g of hair.

After a grace period of 20 minutes at room temperature, the hair was washed with water, squeezed and dried.

Afterwards, the hair was treated with a shampoo wash once, and the hair color was measured using a Minolta CM2600d spectrophotometer (including a reflective component, 10 ° angle, light source D65) in a CIEL ^* a ^* b ^* system.

In this system, L ^* denotes the intensity of the color, a ^* denotes the green / red color axis, and b ^* denotes the blue / yellow color axis.

The lower the L ^* value, the darker or more intense the color. The higher the a ^* value, the more red the hue is, and the higher the b ^* value, the hue becomes more yellowish.

c) Results

The results of coloring for hair containing 90% gray hair are provided in the table below.

The results obtained above show that the association of the triarylmethane dye of formula (I) according to the present invention and the fluorescent dye not selected from cyanide, styryl / hemi cyan, and naphthalimide dyes did not provide a brown color .

IV. A third example of combined application

a) Preparation of the composition

The composition (A4) comprising the triarylmethane dye of formula (I) according to the invention is prepared from the ingredients mentioned in the table below.

The compositions (B6) and (B7) containing the fluorescent dyes according to the present invention were prepared from the components mentioned in the table below.

b) Procedure

The compositions (A4), (B6) and (B7) obtained above were mixed to obtain the following mixtures:

- A4 + B6 with a final concentration of 5 x 10 <" ⁴ > mol%, and

- A4 + B7 with a final concentration of 5 x 10 < ^-4 > mol%.

10 ml of compositions (A4), (B6), (B7), (A4 + B6) and (A4 + B7) were applied to 1 g of hair. The compositions (A4), (B6) and (B7) were also applied at a final concentration of 5 x ^10-4 mol%.

After a grace period of 20 minutes at room temperature, the hair was washed with water, squeezed and dried.

Afterwards, the hair was treated with a shampoo wash once, and the hair color was measured using a Minolta CM2600d spectrophotometer (including a reflective component, 10 ° angle, light source D65) in a CIEL ^* a ^* b ^* system.

In this system, L ^* denotes the intensity of the color, a ^* denotes the green / red color axis, and b ^* denotes the blue / yellow color axis.

The lower the L ^* value, the darker or more intense the color. The higher the a ^* value, the more red the hue is, and the higher the b ^* value, the hue becomes more yellowish.

c) Results

The results of coloring for hair containing 90% gray hair are provided in the table below.

The results obtained above show that the simultaneous application of the triarylmethane dye of formula (I) according to the invention and the fluorescent dye selected from cyanide, styryl / hemi cyan and naphthalimide dyes is very intense and gives a chromatic color .

These results show that the process according to the invention, using only two specific direct dyes, namely triarylmethane dyes of formula (I) in combination with fluorescent dyes, as well as brown collar, which lasts even after 10 shampoo washes, It makes it possible to obtain Brown.

IV. Second Comparative Example of Combined Application

a) Preparation of the composition

The composition (A5) comprising the triarylmethane dye of formula (I) according to the invention is prepared from the ingredients mentioned in the table below.

A composition (B6) comprising a fluorescent dye according to the invention and a composition (B8) comprising a fluorescent dye as defined in the patent application EP 1 133 975 were prepared from the components mentioned in the table below .

b) Procedure

The compositions (A4), (B6) and (B8) obtained above were mixed to obtain the following mixture:

- A5 + B6 at a final concentration of 5 x 10 < ^-4 > mol%, and

- A5 + B8 at a final concentration of 5 x 10 < ^-4 > mol%.

10 ml of compositions (A5), (B6), (B8), (A5 + B6) and (A5 + B8) were applied to 1 g of hair. The compositions (A4), (B6) and (B8) were also applied in a final concentration of 5 x ^10-4 mol%.

After a grace period of 20 minutes at room temperature, the hair was washed with water, squeezed and dried.

Afterwards, the hair was treated with a shampoo wash once, and the hair color was measured using a Minolta CM2600d spectrophotometer (including a reflective component, 10 ° angle, light source D65) in a CIEL ^* a ^* b ^* system.

In this system, L ^* denotes the intensity of the color, a ^* denotes the green / red color axis, and b ^* denotes the blue / yellow color axis.

The lower the L ^* value, the darker or more intense the color. The higher the a ^* value, the more red the hue is, and the higher the b ^* value, the hue becomes more yellowish.

c) Results

The results of coloring for hair containing 90% gray hair are provided in the table below.

The results obtained above show that simultaneous application of a triarylmethane dye of formula (I) and a fluorescent dye selected from cyanide, styryl / hemi cyan and naphthalimide dyes (A5 + B6) according to the present invention is very intense, ≪ / RTI >

These results indicate that the process according to the invention, using only two specific direct dyes, i.e. triarylmethane dyes of the formula (I) in combination with certain fluorescent dyes, makes it possible to obtain a brown color.

By comparison, the association of a triarylmethane dye of formula (I) according to the invention and a fluorescent dye not selected from cyanide, styryl / hemi cyan, and naphthalimide dye (A5 + B8) provides a brown color But only green shades.

Claims (26)

As a method of dyeing keratin fibers, in particular human keratin fibers, such as hair,
(a) a compound selected from the group consisting of compounds of the following general formula (I), optical isomers thereof, geometric isomers thereof, tautomers thereof, organic or inorganic, acid or base salts thereof, solvates thereof such as hydrates, Triarylmethane dyes; And
(b) applying as fluorescent dyes one or more of the components of a fluorescent dye that is a direct dye selected from cyanine dyes, styryl / hemicyanide dyes, naphthalimide dyes, and mixtures thereof,
Wherein said triarylmethane dye (s) (a) and said fluorescent dye (s) (b) are applied together or sequentially to said keratin fibers.
(I)

(In the above formula (I)
R ₁ , R ₂ , R ' ₁ and R ₂ may be the same or different,
Hydrogen atom,
- optionally substituted and / or
- at least one heteroatom, preferably oxygen or sulfur, and / or at least one heteroatom, preferably oxygen, sulfur, C (O), SO, SO ₂ and SO ₃ ^- Linear or branched C ₁ to C ₂₀ alkyl radical, which is interrupted by one or more groups comprising at least one heteroatom selected from N,
A benzyl radical optionally substituted with one or more SO ₃ ^- or SO ₃ H groups;
R ₃ and R ' ₃ may be the same or different and independently of one another:
Linear or branched C ₁ to C ₆ alkyl radicals;
○ sulfonate group SO ₃ ^- , or
A sulfone group SO ₃ H;
N and m may be the same or different and represent two integers ranging from 0 to 4;
Radicals R < ₄ > may be the same or different and independently of one another:
Linear or branched C ₁ to C ₆ alkyl radicals;
○ Hydroxyl radical,
○ SO ₃ ^- ,
○ SO ₃ H,
A halogen atom, preferably a chlorine atom,
Alternatively, two adjacent radicals R ₄ together form an unsaturated six-membered ring, preferably an aromatic ring, such as benzo, optionally substituted with one or more SO ₃ ^- or SO ₃ H groups ;
Q is an integer ranging from 0 to 4;
R ₅ is
Hydrogen atom,
A halogen atom, preferably a chlorine atom,
○ Amino radical,
○ Hydroxyl radical,
An electron-withdrawing group, for example SO ₃ ^- or SO ₃ H, or
Radicals -NR ₆ R ₇ wherein R ₆ and R ₇ , which may be the same or different,
- a hydrogen atom, or
- represents a linear or branched C ₁ to C ₆ alkyl radical;
this is
The radicals R ₂ are present or absent and are symbolized by a dotted bond, and when R ₂ is present, the nitrogen atom having it has a cationic ammonium form and when R ₂ is absent, the nitrogen atom with it is not charged , (+) Does not exist,
● a compound of formula (I) optionally, one or more anion An, to ensure the electrical neutrality of the ^molecule and optionally, comprising at least one cation and M ^+;
- An ^- is an anion, preferably, bromide, chloride, represents a negative ion selected from a mixture of methyl sulfate, toluene sulfonate ion or the ion;
- M ⁺ represents a cation selected from a cation, preferably sodium, potassium, magnesium, calcium, zinc and ammonium ions or a mixture of such ions. The method according to claim 1,
n and m may be the same or different and represent two integers ranging from 0 to 2. < RTI ID = 0.0 > 11. < / RTI > 3. The method according to claim 1 or 2,
R ₁ , R ₂ , R ' ₁ and R' ₂ may be the same or different and independently of one another:
- a hydrogen atom,
- at least one heteroatom selected from oxygen and sulfur and / or a heteroatom selected from at least one heteroatom, preferably oxygen, sulfur, C (O), SO, SO ₂ and SO ₃ ^- A linear or branched C ₁ to C ₆ alkyl radical, preferably an unsubstituted linear or branched C ₁ to C ₆ alkyl radical, optionally substituted and / or optionally interrupted, and, more preferentially, A linear or branched C ₁ to C ₄ alkyl radical, or
- SO ₃ ^- group. 4. The method according to any one of claims 1 to 3,
R ₅ is
- a hydrogen atom,
- SO ₃ ^- group, or
- it represents a radical -NR ₆ R _7, where, R ₆ and R ₇ may be the same or different and independently of one another, a hydrogen atom or a linear or branched C ₁ to C ₆ alkyl radical, and preferably, C ₁ to C ₄ alkyl radical, for example, characterized in that represents the methyl or ethyl radical. 5. The method according to any one of claims 1 to 4,
Characterized in that the triarylmethane dye (s) is cationic and is selected from compounds of the formula (I-cat)
[Formula I-cat]

(In the above formula (I-cat)
R ₁ to R ₅ , and R ' ₁ to R' ₃ , m, n and q are as defined in the above claim, and (I-cat) is understood not to include more than one sulfonate group. 5. The method according to any one of claims 1 to 4,
Characterized in that the triarylmethane dye (s) is anionic and is selected from compounds of the formula (I-an ') or (I-an "):
[Formula I-an '

[Chemical Formula I-an "]

(In the above formula (I-an ') or (I-an "):
R ₁ to R ₅ , and R ' ₁ to R' ₃ , m, n and q are as defined in any one of claims 1 to 4;
- (I-an ') comprises at least two sulfonate groups on ring A, B or C,
- (I-an ") comprises at least one sulfonate group on ring A, B or C,
At least one cation (s) M ⁺ as defined in claim 1 is present to compensate for the anionic charge (s) of the sulfonate group (s). 5. The method according to any one of claims 1 to 4,
Characterized in that the triarylmethane dye (s) is nonionic and is selected from compounds of the formula I-nion:
[I-nion]

(In the above formula (I-nion)
Wherein R ₁ to R ₅ and R ' ₁ to R' ₃ , m, n and q are as defined in any one of claims 1 to 4, and (I-nion) Or < / RTI > not contain any sulfonate groups on C). 8. The method according to any one of claims 1 to 7,
The triarylmethane dye (s) can be prepared by reacting the triarylmethane dye (s) with the following compounds, optical isomers thereof, geometric isomers thereof, tautomers thereof, organic or inorganic, acid or base salts thereof, solvates thereof such as hydrates, ≪ / RTI >

(Y is as defined in claim 1). 9. The method according to any one of claims 1 to 8,
Characterized in that the fluorescent dye (s) (b) is direct and cationic and is selected from styryl or hemicyanine cationic dyes. 10. The method according to any one of claims 1 to 9,
Characterized in that the fluorescent dye (s) (b) is a dye which absorbs light in the yellow, orange and red range, preferably in the range of 400 nm to 500 nm (inclusive of the boundary value), of the absorption wavelength? _Abs . 11. The method according to any one of claims 1 to 10,
Wherein the fluorescent dye (s) (b) is a dye having at least one cationic chromophore selected from the following formula (III), (IV), (IIIa)
Preferably, a fluorophore is m '1 Ar is styryl group -C (R ^d) = C (R ^c) - para to the (di) for a (hydroxy) (C ₁ -C ₆₎ (alkyl ) Amino group, for example, a phenyl group substituted by dihydroxy (C ₁ -C ₄ ) alkylamino, and W ' ⁺ represents an imidazolium or pyridinium group, preferably an ortho- or para- ≪ / RTI > indium.
(III)

(IV)

(In the above formulas (III) and (IV)
W ⁺ particularly represents a cationic heteroaryl group, including quaternary ammonium optionally substituted with one or more (C ₁ -C ₈ ) alkyl groups optionally substituted with one or more hydroxyl groups;
W & apos ^{; +} represents a divalent heteroaryl radical as defined for W ^{& lt; + &} gt ;;
Ar is an aryl group such as phenyl or naphthyl, preferably i) one or more halogen atoms such as chlorine or fluorine; ii) one or more (C ₁ -C ₈₎ alkyl, preferably, C ₁ -C _4, for alkyl groups such as methyl; iii) one or more hydroxyl groups; iv) one or more (C ₁ -C ₈ ) alkoxy groups, for example methoxy; v) one or more hydroxy (C ₁ -C ₈ ) alkyl groups such as hydroxyethyl, vi) one or more amino or (di) (C ₁ -C ₈ ) alkylamino groups, Amino or (di) (C ₁ -C ₈ ) alkylamino group having a C ₁ -C ₄ alkyl moiety optionally substituted with a hydroxyl group, such as (di) hydroxyethylamino, vii) one or more acylamino group; viii) optionally substituted with one or more heterocycloalkyl groups such as piperazinyl, piperidyl or 5-or 6-membered heteroaryl, such as pyrrolidinyl, pyridyl and imidazolidinyl; An aryl group such as phenyl or naphthyl;
Ar ' is a divalent aryl radical as defined for Ar;
M 'represents an integer of 1 to 4, in particular, m' is 1 or 2, more preferably 1;
R ^c and R ^d may be the same or different and represent a hydrogen atom or an optionally substituted (C ₁ -C ₈ ) alkyl and preferably a C ₁ -C ₄ alkyl group or, alternatively, R ^c Is adjacent to W or W 'and / or R ^d is adjacent to Ar or Ar' and forms, together with the atom (s) thereof, (hetero) cycloalkyl, especially R ^c is adjacent to W ⁺ or W ' ⁺ And forms a (hetero) cycloalkyl, such as cyclohexyl;
Q ^- is an organic or inorganic anionic counterion;
(*) Represents the portion of the fluorescent chromophore bound to the remainder of the dye;
Preferably W ⁺ or W & apos ^{; +} is selected from the group consisting of imidazolium, pyridinium, benzimidazolium, pyrazolium, benzothiazolium or quinolinium, optionally substituted by one or more same or different C ₁ -C ₄ alkyl radicals Radical),
≪ RTI ID = 0.0 &

or
(IVa)

(In the above formulas (IIIa) and (IVa)

Represents a bond with a dye,
R ^e , R ^f , R ^g and R ^h , which may be the same or different, are hydrogen atoms or, preferentially, di (C ₁ -C ₆ ) alkylamino or tri (C ₁ -C ₆ ) For example, a (C ₁ -C ₆ ) alkyl group optionally substituted by trimethylammonium. 12. The method according to any one of claims 1 to 11,
Wherein the fluorescent dye (s) (b) is a dyestuff of formula (V), (VI) and (VII) and also an organic or inorganic acid or base salt thereof, optical isomers, geometric isomers and tautomers thereof, , ≪ / RTI > for example, hydrates.
(V)

(VI)

(VII)

(In the above formulas (V), (VI) and (VII)
R ₁ and R ₂ , which may be the same or different, each represent a hydrogen atom or a C ₁ -C ₆ alkyl group; Preferentially represents a hydrogen atom;
G ₁ represents a hydrogen atom or a group selected from NH ₂ and OH;
R _a , R ' _a , R " _a , R" _a , R _b , R' _b , R " _b and R "_'b may be the same or different, a) from the group of a hydrogen atom, b) a halogen atom, to groups: c) _{amino, d) (C 1 -C 4} ) alkylamino, e) (C ₁ - C ₄₎ dialkylamino, f) cyano, g) carboxyl -C (O) OH or the carboxylate ^{-C (O) O -, Q} +, h) hydroxyl -OH or alkoxide -O ^- Q ⁺ , i), (poly) halo (C ₁ -C ₆₎ alkyl, e.g., trifluoromethyl, j) acylamino, k) (C ₁ -C ₆₎ alkoxy, l) (C ₁ -C ₆₎ alkylthio, m) (poly) hydroxy (C ₂ -C _{4) alkoxy, n) (C 1 -C 6} ) _{alkylcarbonyloxy, o) (C 1 -C 6} ) alkoxycarbonyl, p) (C ₁ -C ₆₎ alkylcarbonylamino, q) acylamino, r) _{carbamoyl, s) (C 1 -C 6} ) alkyl-sulfonylamino, t) aminosulfonyl, u) -SO ₃ H or sulfonate -SO ₃ ^- a, Q ^+, or v) (C ₁ -C ₆₎ a group selected from alkoxy, hydroxyl, cyano, carboxyl, amino, (di) (C ₁ -C ₄₎ alkylamino, optionally substituted ( C ₁ -C ₆ ) alkyl, Alternatively, two alkyl radicals having a nitrogen atom of the amino group form a 5- to 7-membered heterocycle optionally containing another nitrogen or non-nitrogen heteroatom; in particular, R _a , R ' _a , R _"a, R"_'a, R _b, R' _b, R _"b and R"_'b is hydrogen or halogen atom or a (C ₁ -C ₄₎ alkyl group, preferably, a hydrogen atom or represents ;
● Alternatively, the two groups on two adjacent carbon atoms, R _a and R _'a; R _b and R ' _b together form a benzo or indeno ring, a fused heterocycloalkyl or a fused heteroaryl group; Benzo, indeno, heterocycloalkyl or heteroaryl ring may be optionally substituted with one or more substituents selected from the group consisting of halogen atoms, amino, (C ₁ -C ₄ ) alkylamino, (C ₁ -C ₄ ) dialkylamino, nitro, cyano, methyl group, an acylamino trifluoromethyl, (C ₁ -C ₄₎ alkoxy (poly) hydroxy (C ₁ -C ₄₎ alkoxy, (C ₁ -C ₄₎ alkylcarbonyloxy, (C ₁ -C ₄₎ Alkoxycarbonyl or (C ₁ -C ₄ ) alkylcarbonylamino radical, an acylamino, a carbamoyl or alkoxyalkylsulfonylamino radical, an aminosulfonyl radical, or (C ₁ -C ₆ ) alkoxy, hydroxyl, (C ₁ -C ₆ ) alkyl radical optionally substituted by halogen, cyano, carboxyl, amino, (C ₁ -C ₄ ) alkylamino and (C ₁ -C ₄ ) dialkylamino, or alternatively , The two alkyl radicals in the nitrogen atom of the amino group may be replaced by a 5 to 7 membered heteroaromatic ring optionally containing another nitrogen or non- And forming a cycle; First, R _a and R ' _a together form a benzo group;
● Alternatively, the two groups R _i and R _a; And / or the groups R ' _i and R ≈ _a together form (fused) fused cycloalkyl, preferentially cycloalkyl, for example, cyclohexyl;
R _g represents a hydrogen atom, an optionally substituted (hetero) aryl (C ₁ -C ₄ ) alkyl group or a (C ₁ -C ₆ ) alkyl group; Preferentially, R _b represents a hydrogen atom or a (C ₁ -C ₃ ) alkyl or benzyl group;
R _e represents a covalent, linear or branched, optionally substituted (C ₁ -C ₈ ) alkylene or (C ₂ -C ₈ ) alkenylene hydrocarbon-based chain, preferably R _e is Unsubstituted (C ₁ -C ₆ ) alkylene;
● R _f is a hydrogen atom, (C ₁ -C ₄₎ alkoxy group, an amino group R ₃ R ₄ N-, ₄ quaternary ammonium groups _{M ', R 3 R 4 R} 5 N + - represents the, here, R _3, R ₄ and R ₅ may be the same or different and represent a (C ₁ -C ₄ ) alkyl group, or R ₃ R ₄ N- is an optionally substituted heteroaryl group, preferentially an optionally substituted imidazolyl Or alternatively M ', R ₃ R ₄ R ₅ N ⁺ - represents an optionally substituted cationic heteroaryl group, preferentially imidazolyl optionally substituted with a (C ₁ -C ₃ ) alkyl group, Lt; / RTI >
G is an i) group -NR _c R _d , ii) -OR where R is a) a hydrogen atom, b) an optionally substituted, preferentially unsubstituted (C ₁ -C ₆ ) alkyl group, c ) optionally substituted (hetero) aryl group, d) an optionally substituted (hetero) aryl (C ₁ -C ₆₎ alkyl group, e.g., benzyl, e) an optionally substituted (hetero) cycloalkyl, f ) represents optionally substituted (hetero) cycloalkyl (c ₁ -C ₆₎ alkyl, in accordance with certain embodiments, G is a group -NR _c R _d denotes a, in accordance with certain embodiments other examples, G is a (c ₁ -C _6), or represent an alkoxy group;
Alternatively, when G represents -NR _c R _d , the two groups R _c and R ' _a and / or R _d and R _a together are optionally substituted with one or more (C ₁ -C ₆ ) alkyl groups Form a 5- to 7-membered heterocycle containing one or two heteroatoms selected from saturated heteroaryl or heterocycle, preferentially nitrogen and oxygen; More preferably, the heterocycle is selected from morpholinyl, piperazinyl, piperidyl and pyrrolidinyl groups;
R _c and R _d may be the same or different and are hydrogen atoms or a) optionally substituted (hetero) aryl such as phenyl, b) optionally substituted (hetero) aryl (C ₁ - c ₄₎ alkyl, c) an optionally substituted (hetero) cycloalkyl, d) an optionally substituted (hetero) cycloalkyl (c ₁ -C _{4) alkyl, f) (c 2 -C 5} ) alkyl, or g) an optionally substituted (C ₁ -C ₈₎ alkyl, preferably, hydroxyl, carboxyl, carboxylate, optionally substituted with sulfate or sulfonate, (C ₁ -C _8), or represents a group of alkyl;
Alternatively, two adjacent radicals R _c and R _d at the same nitrogen atom together form an optionally substituted heterocyclic or an optionally substituted heteroaryl group;
R _i and R ' _i may be the same or different and represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group;
●

(Hetero) aryl group fused to a phenyl ring, or, alternatively, absent from the phenyl, or, preferentially, when the ring is present, the ring is benzo;
M is an integer from 1 to 18, in particular an integer from 1 to 14; Preferentially, an integer of 2 to 10; More preferably, an integer of 3 to 8; More specifically, an integer of 4 to 6;
M represents an anionic counterion derived from a salt of organic or inorganic acid, which ensures the electrical neutrality of the dye, or from an organic or inorganic base;
Q ⁺ represents a cationic counterion, for example an alkali metal, an alkaline earth metal or ammonium, derived from an organic or inorganic acid salt which ensures electrical neutrality of the dye or from an organic or inorganic base;
When the dye comprises a carboxylate, sulfonate or alkoxide group, it is understood that M 'and Q ⁺ may not be present to ensure the electrical neutrality of the dye. 13. The method according to any one of claims 1 to 12,
The fluorescent dye (s) (b) can be prepared from styryl dyes of the formula (VIII), and also organic or inorganic acid or base salts thereof, optical isomers, geometric isomers and tautomers thereof and solvates thereof, Characterized in that:
(VIII)

(In the general formula _{(VIII), G, G 1} , R a, R 'a, R "a, R b, R' b, R" b, R i, R 'i, R 1, R 2 and m are As defined in the claims above,
Preferably,
R ₁ and R ₂ may be the same or different and represent a hydrogen atom;
R _i and R ' _i may be the same or different and represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group, preferably hydrogen;
R _a , R ' _a and R " _a may be the same or different and each represents a hydrogen atom, a halogen atom such as fluorine, or -OH, -O ^- Q ⁺ , (C ₁ -C ₆ ) Nitro, or cyano group, Q ⁺ is as defined in the above claim;
R _b , R ' _b and R " _b may be the same or different and represent a hydrogen atom or a (C ₁ -C ₆ ) alkyl group;
● Alternatively, two adjacent radicals R _b and R _'b, together with the carbon atom having this that, to form a condensed or fused benzo groups pyridinium, wherein the benzo groups may be substituted, and; Preferably, said benzo group is unsubstituted;
G represents an optionally substituted, preferentially unsubstituted group -NR _c R _d or a (C ₁ -C ₆ ) alkoxy group; According to certain embodiments, G represents a group -NR _c R _d , according to another particular embodiment G represents a (C ₁ -C ₆ ) alkoxy group;
R _i and R ' _i , which may be the same or different, each represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group,
●

Represents an aryl or heteroaryl group fused to a phenyl ring; Alternatively, is not present at the phenyl ring; Preferentially, when a ring is present, the ring is benzo;
M represents an integer of 1 to 18; In particular an integer from 2 to 16; Preferentially, an integer of 3 to 10; More preferably, an integer of 4 to 6;
R _c and R _d may be the same or different and represent a hydrogen atom, a (C ₂ -C ₄ ) alkyl group or a substituted (C ₁ -C ₈ ) alkyl group, _{, ii) (C 1 -C 3} ) alkoxy, iii) hydroxyl, and iv) (C ₁ -C ₃₎ by at least one group selected from an alkyl-carbonyl, preferably, substituted with one or more hydroxy (C ₂ - C ₄ ) alkyl;
M 'represents an anionic counterion derived from an organic or inorganic acid salt or from an organic or inorganic base which ensures the electrical neutrality of the dye;
It is understood that when the dye comprises an alkoxide group, M 'and Q ⁺ may not be present to ensure the electrical neutrality of the dye). 14. The method according to any one of claims 1 to 13,
The fluorescent dyes (s) (b) may be prepared from styryl dyes of the formula (IX) and also organic or inorganic acid or base salts thereof, optical isomers, geometric isomers and tautomers thereof and solvates thereof, Characterized in that:
(IX)

(IX), G, G ₁ , R _a , R ' _a , R _b , R' _b and m are as defined in claim 12 or 13). 15. The method according to any one of claims 1 to 14,
Wherein the fluorescent dye (s) (b) is selected from the group consisting of compounds of the following formula (X), (XI), (XII) and (XIII) and their organic or inorganic acid or base salts, their optical isomers, geometric isomers and tautomers Isomer, and a solvate thereof, for example, a hydrate.
(X)

(XI)

(XII)

(XIII)

(In the above formulas (X), (XI), (XII) and (XIII)
R ¹ , R ² , R ³ and R ⁴ may be the same or different and represent a hydrogen atom or a (C ₁ -C ₆ ) alkyl group; Preferably, R ² and R ³ represent a hydrogen atom, R ¹ and R ⁴ may be the same or different and represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group;
^{● R 5, R 6, R} 7, R 8 and R ⁹ are, may be the same or different, i) hydrogen atom or ii) a halogen atom, e.g., Cl, Br or F, iii) group OR (where , R is a hydrogen atom or a Q ⁺ or a (C ₁ -C ₃ ) alkyl group as defined in claim 13), a group from the groups iv) aryl, such as benzene, v) aryl C ₁ -C ₃₎ alkyl, e.g., benzyl, vi) cyano, vii) _{nitro, viii) (C 1 -C 3} ) alkylthio, ix) amino NR ¹⁰ R ¹¹ (wherein, R ¹⁰ and R ¹¹ May be the same or different and are a) hydrogen atom, b) (C ₂ -C ₄ ) alkyl group or c) substituted (C ₁ -C ₈ ) alkyl group, preferably one or more groups selected from It refers to an optionally substituted (C ₂ -C ₄₎ alkyl:
- cyano,
- (C ₁ -C ₃₎ alkoxy,
-Hydroxyl, and
- alkyl-carbonyl (C ₁ -C _3);
In particular, R ¹⁰ and R ¹¹ may be the same or different and are each a hydrogen atom or a (C ₁ -C ₆ ) alkyl group substituted by one or more hydroxyl, cyano or (C ₁ -C ₃ ) alkylcarbonyl groups, For example, hydroxyethyl;
M is an integer from 1 to 18; In particular an integer from 2 to 16; Preferentially, an integer of 3 to 10; More preferably, an integer of 4 to 6;
M 'represents an anionic counterion as defined in claim 13;
When the dye comprises an alkoxide group, it is understood that M 'and Q ⁺ may not be present to ensure the electrical neutrality of the dye). 16. The method according to any one of claims 1 to 15,
The fluorescent dye (s) (b) of the present invention are selected from compounds of the following formulas (XIV) and (XV):
(XIV)

(XV)

(XIV) and (XV), R ⁵ , R ⁷ , R ⁸ and m are as defined in claim 15, and in particular,
R ⁵ and R ⁸ may be the same or different and each represents a hydrogen atom or a (C ₁ -C ₄ ) alkoxy group such as methoxy, preferably, R ⁵ and R ⁸ represent a hydrogen atom;
R ⁷ represents a (C ₁ -C ₄ ) alkoxy group or NR ¹⁰ R ¹¹ , wherein R ¹⁰ and R ¹¹ may be the same or different and are a) a hydrogen atom or b) i) hydroxyl, ii ) RZC (X) -Y- wherein X, Y and Z represent an oxygen or sulfur atom or N (R ') or alternatively X and / or Z represents a bond, R and R' And R 'may be the same or different and represent a hydrogen atom or a (C ₁ -C ₆ ) alkyl group, preferably X represents an oxygen atom, iii) sulfone SO ₃ H, iv) sulfonate SO ₃ ^-, Q ^+, v) carboxylate, C (O) O ^-, Q ⁺ (wherein, Q ⁺ is optionally substituted with one or more groups selected from represents a cationic counter ion, for example, alkali metal or alkaline earth metal) a (C ₁ -C ₈₎ represents an alkyl; In particular, R ⁷ represents a group NR ¹⁰ R ¹¹ , wherein R ¹⁰ and R ¹¹ may be the same or different and are a) a hydrogen atom or b) i) hydroxyl, ii) carboxyl, iii) carboxyl (C ₁ -C ₆ ) alkyl group optionally substituted with one or more groups selected from the group consisting of: (a) a hydroxyl group; (b) a hydroxyl group; acid, and iii) represents an optionally substituted (C ₁ -C ₆₎ alkyl with one or more groups selected from carboxylate;
M is an integer from 1 to 18; Especially an integer of 1 to 6; Preferentially, an integer of 1 to 4; More preferably, an integer of 1 to 2;
M 'represents an anionic counterion derived from an organic or inorganic acid salt or from an organic or inorganic base which ensures the electrical neutrality of the dye;
It is understood that when the dye comprises a sulfonate or carboxylate group, M 'and Q ⁺ may not be present to ensure the electrical neutrality of the dye). 16. The method of claim 15,
The fluorescent dye (s) (b)
(X) having the following substituents, and also organic or inorganic or basic salts thereof, optical isomers, geometric isomers and tautomers thereof, and solvates thereof, for example hydrates:

(XI) having the following substituents, and also their organic or inorganic acid or base salts, their geometric isomers and tautomers, and their solvates, e. G., Fluorescent dyes of hydrates:

(Fluorescent) dyes of the following formulas (X ') and (XI') having the following substituents and also organic or inorganic acids or base salts thereof, their geometric isomers and tautomers, and solvates thereof,
[Formula X '

(XI ')

(Wherein M 'is as defined in the above claim)
(XII) having the following substituents, and also organic or inorganic or basic salts thereof, optical isomers, geometric isomers and tautomers thereof, and solvates thereof, for example hydrates:

(XIII) having the following substituents, and also organic or inorganic acid or base salts thereof, their geometric isomers and tautomers, and solvates thereof, e.g., fluorescent dyes of hydrates: and

(XII ') and (XIII') having the following substituents and also fluorescent dyes of organic or inorganic acids or base salts thereof, their geometric isomers and tautomers, and solvates thereof, for example hydrates :
[Formula XII ']

[Formula XIII ']

Preferably, the fluorescent dye (s) (b) is selected from the following compounds and also their organic or inorganic acid or base salts, their geometric isomers and tautomers, and their solvates, for example hydrates Way:

Wherein M 'and Q ⁺ are as defined in the above claims. 18. The method according to any one of claims 1 to 17,
(Iii) a reducing agent of formula (XVI), and further addition salts thereof and mixtures thereof, ii) thioglycolic acid, iii) thiolactic acid, iv) glyceryl monothioglycol Vii) cysteine, ix) N-acetylcysteine, x) thiomalic acid, xi) pantothene, xii) aminopropyltrimethoxysilane, Dimercaptosuccinic acid, xiii) N- (mercaptoalkyl) -ω-hydroxyalkylamide, xiv) N-mono- or N, N-dialkylmercapto-4-butyramide, Xvii) N- (mercaptoalkyl) succinimide derivatives, xviii) alkylaminomercaptoalkylamides, xix) 2-hydroxypropyl thioglyconate And (2-hydroxy-1-methyl) ethyl thioglycolate, xx) mercaptoalkylaminoamide, xxi) N-mercaptoalkylalkanediamide, xxii ) ≪ / RTI > formamidinesulfonic acid derivatives, addition salts thereof, and mixtures thereof.
(XVI)

(In the above formula (XVI):
X represents P, S or SO ₂ ,
- q represents an integer of 0 or 1,
- t represents an integer of 1 or 2,
R is optionally interrupted by a heteroatom and / or is selected from the group consisting of hydroxyl, halo, amine, carboxyl, ((C ₁ -C ₃₀ ) alkoxy) carbonyl, amido, ((C ₁ -C ₃₀ ) Linear or branched, saturated or unsaturated C ₁ to C ₆ alkyl optionally substituted with one or more radicals selected from the group consisting of (C ₁ -C ₃₀ ) acyl) amino, mono or dialkylamino, and mono- or dihydroxylamino radicals. It represents a C ₂₀ alkyl radical). 18. The method according to any one of claims 1 to 17,
Characterized in that no reducing agent is used. 20. The method according to any one of claims 1 to 19,
(B) the triarylmethane dye (s) (a) according to any one of claims 1 to 8 and the fluorescent dye (s) according to any of claims 1 and 9 to 17, Are applied together to the keratin fibers; Preferably, the process comprises the steps of: a) adding to the keratin fiber a compound of formula (I) as defined in any one of claims 1 to 8 and its optical isomer, its geometric isomer, its tautomer, One or more triarylmethane dyes (a) selected from organic or inorganic acid or base salts, solvates thereof, for example hydrates, and mixtures thereof, and one or more of the compounds according to any one of claims 1 and 9 to 17 Characterized in that it comprises applying a cosmetic composition comprising at least one fluorescent dye (b) as specified. 20. The method according to any one of claims 1 to 19,
- a first step of applying to the keratin fiber a cosmetic composition comprising at least one fluorescent dye (b) as defined in any of claims 1 and 9 to 17,
(I) as defined in any one of claims 1 to 8 and its optical isomers, its geometric isomers, its tautomers, its organic or inorganic, acid or base A second step of applying a cosmetic composition comprising at least one triarylmethane dye (a) selected from a salt, a solvate thereof, for example a hydrate, and mixtures thereof, comprising at least the two successive steps ≪ / RTI > 20. The method according to any one of claims 1 to 19,
(I) as defined in any one of claims 1 to 8 and its optical isomers, its geometric isomers, its tautomers, its organic or inorganic acids, or its salts, A first step of applying a cosmetic composition comprising at least one triarylmethane dye (a) selected from a base salt, a solvate thereof, for example, a hydrate, and a mixture thereof,
- a second step of applying to the fiber a cosmetic composition comprising at least one fluorescent dye (b) as defined in any of claims 1 and 9 to 17, RTI ID = 0.0 > 1, < / RTI > 23. The method of claim 21 or 22,
Characterized in that it comprises at least two successive steps wherein the pH of the cosmetic composition (s) is from 6 to 11, in particular from 7 to 10, more preferentially from 7.5 to 9.5, and more preferably from 9 to 9.5. 9. A compound of formula (I) according to any one of claims 1 to 8, as well as its optical isomers, its geometric isomers, its tautomers, its organic or inorganic acid or base salts, its solvates, (B) one or more triarylmethane dyes (a) selected from the group consisting of hydrates, hydrates, and mixtures thereof, and one or more fluorescent dyes (b) as defined in any one of claims 1 to 9. As a composition,
The composition optionally has a pH of 6 to 11, especially 7 to 10, and more preferably 7.5 to 9.5, and more preferably 9 to 9.5. 9. A compound of formula (I) according to any one of claims 1 to 8, as well as its optical isomers, its geometric isomers, its tautomers, its organic or inorganic acid or base salts, its solvates, A first compartment containing one or more triarylmethane dyes (a) selected from the group consisting of hydrates, hydrates, and mixtures thereof, and one or more fluorescent dyes as defined in any one of claims 1 and 9-17. (b). < Desc / Clms Page number 13 > It is possible to use bright keratin fibers, in particular human keratin fibers, such as hair, for example, chestnut-brown, dark chestnut-brown, brown, shiny brown (for example), without the use of additional dyes in addition to the triarylmethane dye (a) (I) as defined according to any one of claims 1 to 8 for dyeing, or even black, and also optical isomers thereof, geometric isomers thereof, tautomers thereof, organic or inorganic acids thereof, Of any one of claims 1 and 9 to 17 in combination with one or more triarylmethane dye (s) (a) selected from a base salt, a solvate thereof, for example a hydrate, Use of at least one fluorescent dye (s) (b) as defined in accordance with paragraph [